Temperature indicating compositions of matter

ABSTRACT

Novel and stable compositions of matter are disclosed which change color sharply upon a transition from a liquid state to a solid state or from a solid state to a liquid state, which change of state is at substantially a predetermined temperature corresponding to a temperature to be measured. 
     The constituents of the novel compositions of matter comprise: 
     1. a solvent (I) consisting of a single substance or a mixture of substances and adapted to change from a solid state at substantially a predetermined temperature to a liquid state and 
     2. an indicator system (II) consisting of one or more substances different from (I), characterized in that 
     (a) (II) is soluble in (I) when the latter is in the liquid phase, and 
     (b) (II) changes color visible to the naked eye when (I) passes from the solid to the liquid phase or from the liquid to the solid phase. 
     Thermometers containing said stable compositions of matter are also disclosed.

RELATED APPLICATIONS

This application is a continuation of U.S. Ser. No. 946,935, filed Sept.28, 1978, which is a continuation-in-part of U.S. Ser. No. 895,422,filed Apr. 13, 1978, abandoned in favor of Ser. No. 946,935, now U.S.Pat. No. 4,232,552 which is a continuation-in-part of U.S. Ser. No.844,334, filed Oct. 21, 1977, abandoned in favor of Ser. No. 895,422,which is a continuation-in-part of U.S. Ser. No. 796,492, filed May 12,1977, abandoned in favor of Ser. No. 844,334, all entitled "TEMPERATUREINDICATING COMPOSITIONS OF MATTER," for which benefit is claimed under35 USC §120. This application is also related by subject matter to (1)U.S. Ser. No. 869,406 (Ulin), filed Jan. 16, 1978, now U.S. Pat. No.4,128,007, entitled "SUPPORT MEMBER FOR A DISPOSABLE THERMOMETER",disclosing a rectal adapter similar to that described in the DESCRIPTIONOF THE PREFERRED EMBODIMENTS below and FIGS. 14-16 herein, and (2) anapplication entitled "TEMPERATURE INDICATING DEVICE USING A PRESSURESENSITIVE ADHESIVE SEAL", Ser. No. 896,114 by E. A. Giezen, G. D. B. vanHouwelingen and M. Cramer, filed on Apr. 13, 1978, now U.S. Pat. No.4,198,942 and based upon Netherlands Application No. 7,704,765 filed May2, 1977 in the Netherlands, both (1) and (2) incorporated herein.

BACKGROUND OF THE INVENTION

1. Field of the Invention

The invention relates to the field of temperature-indicatingcompositions and devices therefor, and in particular, the sub-fields ofdisposable thermometers and compositions of matter which changecharacteristics with change in phases for use in disposablethermometers.

2. Description of the Prior Art

For many years the conventional mercury thermometer has been the primarytemperature-indicating device which has been used in clinicalapplications for the measurement of temperature in the human body andother animal bodies, and for the measurement of temperature of gases,liquids, and even solids in commercial and industrial applications.However, as will be readily discerned by the observer, this type ofthermometer has numerous disadvantages inherent in the nature ofmercury, a poisonous substance to humans and other animals, andconstruction of the mercury thermometer with the placement of mercurywithin fragile glass. First, in clinical applications involving humansand other animals, several minutes, usually at least three, are requiredto obtain a meaningful temperature reading. Second, once used, theconventional mercury thermometer because of its extraordinary expensemust be sterilized before the next clinical application. Suchsterilization and resterilization often involve substantial labor costs,whether in hospitals, physicians' offices, homes, or in the field.Third, in hospital use, inevitable human error in the sterilization ofthermometers presents the ever-occurring substantial probabilities ofoutbreaks of contagious diseases such as hepatitis. Fourth, thebreakable nature of the mercury thermometer is an ever-present dangerwhen considering the poisonous nature of mercury, especially in thepresence of children. Fifth, in industrial applications, especiallyinvolving the determination of relatively high temperatures in vesselslocated in plants and refineries, the user must ordinarily reach intoinexcessible places to locate the thermometer, and because of theextreme difference between said relatively high temperatures and theoutside ambient temperature, readings from conventional thermometers areoften in extreme error seconds after the withdrawal of the mercurythermometer.

Accordingly, for many years persons have attempted to construct aninexpensive device of mixtures or materials of any kind which wouldchange in some characteristic visible to the naked eye at substantiallythe temperature to be measured so that the inconveniences of theconventional mercury thermometer could be avoided. For instance, Ramsdenin British Pat. No. '3640 (1897) provided a piece of paper, celluloid,metal or other suitable material which would be (1) coated with, or (2)formed with a hollow or recess containing a substance, mixture ofmaterial which would change in opacity at the temperature for theindication of which the appliance is intended to be used (see page 1,lines 24-38; page 5, lines 23-45 of '3640). Ramsden desired a substanceor material (see page 2, lines 9-23) that would change in color at thepredetermined temperature, but did not indicate any in hisspecification; he only indicated several substances, generally fattyacids, which would change in opacity or change from being opaque totransparent upon change in phases from solid to liquid or vice versa(see page 3, lines 11-18), so that indicator layers, dyes, etc., wouldhave to be employed in the device.

After Ramsden, the art primarily pursued only those heat-sensitivesubstances which would change from being opaque to transparent at thephase interface in devices (hereinafter described as "opaquethermometers") that would employ indicator layers having dyes that wouldonly be apparent when the heat-sensitive substance had changed fromopaque to transparent and would mix with the heat-sensitive compoundsupon a change in phases. For example, U.S. Pat. No. 3,175,401 issued toGeldmacher (1965) describes a thermometer with several cavities, eachcontaining a different thermally-indicating composition melting at adifferent temperature range. Each of the thermally-indicatingcompositions employed by Geldmacher is normally opaque below a certaintemperature and transparent above a certain temperature, similar toRamsden's compositions of matter. The temperature indication is obtainedby a complete change of state of the thermally responsive material ineach cavity. Furthermore, as many as forty to fifty different chemicalcompounds would be necessary to cover the desired human clinicaltemperature range of 96° F. to 105° F., so that Geldmacher's device wasprohibitively expensive to manufacture for mass consumer use; likewise,the availability of these compounds at 0.2° F. or 0.1° C. increments wasnot disclosed.

Another type of temperature indicating device was disclosed in U.S. Pat.No. 3,465,590 (1969) to Kluth, et al. The teaching describes athermometer which is disposable after a single application and does notemploy mercury as the thermally responsive substance. Rather, Kluth, etal., employed mixtures of certain of the even series of saturated fattyacids, [perhaps] suggested by the Ramsden materials on page 3, lines11-18 of '3640), to wit, myristic acid, palmitic acid and lauric acidfor indication of temperature of the human body within plus or minus1/2° F. Again, as in Geldmacher, the device of Kluth measured andindicated temperature by a complete change of state of thethermally-responsive material in each cavity. Although the use ofKluth's thermometer obviated some of the deficiences of the conventionalmercury thermometer, its application was limited to temperaturemeasurements in the range of about 96° F. to about 101° F., and theaccuracy was restricted explicitly in Kluth to plus or minus 1/2° F.,thus precluding Kluth from use for more precise the temperaturemeasurements and replacement of the conventional mercury thermometer. Asa practical matter, such Kluth instruments did not provide accurateclinical information regarding the temperature of the human or animalbody during a period of fever when the temperature was frequently above101° F., as the human body is often (102° F.-105° F.) during highfevers. Another difficulty with the Kluth thermometer was that anaccurate temperature determination really depended on a complete changeof state of the solid solution employed as the thermally-responsivematerial. While Kluth intended for each cavity in his thermometer tohave three stages of melting (each stage represented an indication ofplus or minus 1/2° F.), some experience by the user were necessary inorder to determine which stage a cavity was in if it was melting. Moreprobably, if the cavity responding to the closest temperature of thehuman or animal body to be measured did not completely change state,certain nucleation sites remained in the cavity so that the cavityrapidly solidified, causing an inaccurate measurement as withdrawal ofthe thermometer was followed by quick solidification of the cavitiesonly partially liquified or containing appreciable nucleation sitesbecause of impurities, etc. The complete change of state necessary,i.e., from opaque solid to translucent liquid, in addition to theinherent 1/2° F. inaccuracy and the 101° F. limitation of the devicemade the Kluth thermometer inadequate to replace the conventionalmercury thermometer (admitted by Kluth in Column 2, lines 70-73 andColumn 3, lines 1-8 of U.S. Pat. No. 3,465,590).

Still another type of thermometer was described by Finklestein in U.S.Pat. No. 3,521,489 (1970). The temperature indication in this type ofthermometer is based upon the flow of a melted material from so-called"holding compartment" into a so-called "flow-inducing receiving element"such as the adsorbent material, by a capillary action (see Column 1,lines 61-72 of '489). As in the Geldmacher patent, however, temperatureindication was realized by the use of numerous different thermallyresponsive chemical compounds, each undergoing a complete change ofstate at a different predetermined temperature with a correspondingchange from opaque to transparency. It was obvious once again that withthe employment of any "classical" material changing from opaque totransluscent at the phase change, some indicator dye or material at thebottom of a cavity would have to be placed in order to indicate readilyto the observer the change in state of the composition of matterindicating the temperature to be determined. See also Crites U.S. Pat.No. 3,580,079 (1971) which required the transparent state of thetemperature responsive material to be of the same index of refraction ofa roughened window in order to optically smooth the window.

As the search continued for a disposable clinical thermometer to replacethe conventional mercury thermometer, Weinstein and Sagi in U.S. Pat.No. 3,631,720 disclosed a specific device employing a carrier sheet (11in '720) with a plurality of individual temperature-indicating elementsdistributed over at least one surface of the carrier sheet in the formof a grid with the elements buried in a corresponding number of cavities(located between the sheet 11 and surfaces 20A and 10A), each element 12having an opaque layer covering an indicator element 20. Upon melting ofthe coatings 22 in '720, the indicator material 20 would be exposed tothe observer. The drawback of '720 was that the manufacturer of amultilayered device as shown in FIG. 4 of '720 with a "sandwich"indicator means 20 in temperature-indicating elements 12 becameexpensive.

In U.S. Pat. No. 3,946,612 (1976) to Sagi and Weinstein, thespecification disclosed the use of a heat conducting carrier having aplurality of spaced cavities with a corresponding plurality of solidsolutions each comprising an organic layer of at least two differentorganic chemicals (ortho-chloronitrobromobenzene andortho-bromonitrobromobenzene) in varied composition ratios deposited insaid cavities that would turn from opaque to clear upon a change inphase from solid to liquid. This organic layer (9 in '612) formed asandwich for an indicator layer (13 in '612) between it and a masking oropaque layer (15 in a multilayered device similar to U.S. Pat. No.3,665,770). When the cavity of FIG. 2 of '612 was heated to apredetermined temperature, the composition of matter would change from asolid to a liquid state, permeating the indicator 13 and forcing a dyeinto the opaque layer to change the color of said opaque layer to thecolor of the dye. Several problems were presented in the construction ofthe '612 multilayered device: first, such a device with three internallayers in the cavity and two transparent external layers was hard tomanufacture and very expensive. Second, sometimes the organiccomposition would not totally change from liquid to solid, so thatnucleation sites remained in the organic layer 9; hence,resolidification quickly occurred upon withdrawal of the thermometer,and not all the dye was forced into the upper or opaque layer 15. Third,because of the size of the layers, it was sometimes hard to visualizethe change in color when only some of the dye was transferred into thepreviously opague layer. For other examples of "opaque" thermometers,see Keele, U.S. Pat. No. 3,859,856 (with "supercoolable" inorganiccompounds, column 4, lines 50-54); Loconti, U.S. Pat. No. 2,928,791(dyes employed with solvents of Table I); Gignilliat III, U.S. Pat. No.3,430,491 (physical movement of heat-sensitive solvent upon melting into"absorbent backing" layer with different color, column 7, lines 54-59);Roszkowski, U.S. Pat. No. 3,785,336 (methyl sterate); Godsey, Jr., U.S.Pat. No. 3,980,581 ("nucleating" agents to limit or reduceundercooling); Wahl, et al., U.S. Pat. No. 3,002,385; Fryar U.S. Pat.No. 3,597,976; Lang, U.S. Pat. No. 3,677,088 ("spacer layer" betweenindicator layer and heat-sensitive material); Pickett, U.S. Pat. No.3,704,985 (ortho-chloronitrobenzene:ortho-bromonitrobenzeneheat-sensitive material, but no "space layer"); Chadha, U.S. Pat. No.3,712,141 ("space layer"); Pickett, U.S. Pat. No. 3,765,243("self-firing thermometer" with exothermic reaction betweenheat-sensitive material and dye); Godsey, U.S. Pat. No. 3,774,450("frangible" spacer layer to be crushed before application); Pickett,U.S. Pat. No. 3,826,141; Ayres, U.S. Pat. No. 3,922,917 (avoids "cover"layer by means of crushable dome); Pecorella, U.S. Pat. No. 3,929,021;Chadha, U.S. Pat. No. 3,956,153; Sagi, U.S. Pat. No. 3,835,990, Keele,U.S. Pat. No. 3,859,856; Sagi et al., U.S. Pat. No. De. 238,661 (1976);Nollen, U.S. Pat. No. 3,895,523; Chilton, U.S. Pat. No. 3,998,098; andPickett, U.S. Pat. No. 3,871,232.

The phenomena of undercooling encountered with various heat responsivematerials in passing from liquid to solid is taught in Chadha, U.S. Pat.No. 3,956,153 to be minimized by incorporation of predetermined amountsof a regenerative nucleating agent partially or wholly soluble in somedegree in the heat responsive materials.

Another form of device in another art and not to be confused with the"pure" thermometer (this is used only for measurement of temperature) isthe "time-temperature" thermometer or "time-temperature" watch whichindicates by integration of time and temperature a property of asubstance (such as deterioration of meat due to elevated temperature).For example, Chapman in U.S. Pat. No. 2,195,395 teaches the measurementof the thermal abuse of frozen food by indicating whether or not achemical reaction has proceeded past a certain point through ameasurement of the change in pH, using a dye in water. A major advancein such an art was Larsson, U.S. Pat. No. 3,946,611, whereinparaformaldehyde 19 in FIG. 2 decomposes at a rate which is a functionof temperature to produce formaldehyde gas that permeats throughmembrane 22 to contact a wick means 18 which contains hydroxyaminehydrochloride and a dye and low volatile acid. After an accumulation oftime the HCl lowers the pH of wick means 18 so that the dye and wickchange color (see Example 3). The color change does not indicate achange in color upon change in phases of a solvent. See also Gessler,U.S. Pat. No. 3,065,083 describing a time-temperature indicator toindicate the presence of fatty acids for frozen food packages; U.S. Pat.No. 3,437,070 to Campbell; and U.S. Pat. No. 3,479,877 to Allen.

Still another type of device in still another art and not to be confusedwith the "pure" thermometer is a device employing "liquid crystals"--a"liquid" which, although turning color in a specific range oftemperatures (usually in a range of 11/2° F.-2° F. and no better than1/2° F.) because of a change in orientation of the liquid, is notsuitable for thermometry because the "liquid" is incapable ofsupercooling, therefore resolution at better than 1/2° F. is difficultand the device must be read immediately upon withdrawing the "liquidcrystal" device from the subject. Examples of "liquid crystal" devicesand sprays and related technology are Sanford, U.S. Pat. No. 3,633,425;Flam, U.S. Pat. No. 3,661,142 (accuracy only within 2° C.); Parker, U.S.Pat. No. 3,898,354; Suzuki, U.S. Pat. No. 3,974,317; and Davis, U.S.Pat. No. 3,619,254.

A state of the art method for depositing precisely metered quantities ofliquid on a small surface is revealed in Pickett et al., U.S. Pat. No.3,810,779.

Japanese Patent Applications Nos. 47-34735 and 50-105555 show,respectively, compositions (1) comprising a dye and an acid with apolymeric material, and (2) a dye, an acidic compound, and a solventwhich change colors although not at the melting point of the solvent.

Some abbreviated attempts have been made to find substances that wouldchange color upon change in phases for use in thermometers, but nonehave been able to overcome the combined problems of employing manydifferent unrelated compounds, accidental overheating, etc. For example,Jennings in U.S. Pat. No. 2,261,473 combines certain cognizable, organicdyes (page 2, column 2, lines 13-28) with certain solvents (page 2,column 1, lines 56-60) wherein the change in pH changes the color of thedyes, but needs, like Kluth, 45 or 50 different compositions over arange such as the human clinical range. A major advance in the art isRenbaum, U.S. Pat. No. 3,700,603 wherein no solvent system is employed,but the organic moieties ("electron donors" and "electron acceptors") dochange color upon change in phases (see Table I, columns 5 and 6).However, because Renbaum apparently did not attempt to find a suitablesolvent system for his electron donor-acceptor pairs, a number ofdifferent parts would be needed for almost any temperature range to bedetermined, e.g., the same problems as Kluth appeared. See also Hammond,U.S. Pat. No. 3,576,604, who also does not use a solvent over a range oftemperatures.

An inexpensive disposable thermometer was needed and intensely desiredin the thermometer industry which would be easily constructed and havematerials which would change some characteristics visible to the nakedeye but not readily susceptible to quick reversibility upon withdrawalfrom the source whose temperature was to be measured. If one couldprovide a chemical substance that would change in color in and of itselfupon change in phases, the use of dyes in indicator layers would beeliminated. Likewise, a disposable thermometer was needed to magnify thepresence of an indicator layer in cases involving "classical" substancesthat changed only from opaque to transparent upon change in phase fromsolid to liquid.

MISCELLANEOUS

In an unpublished and short memorandom of June, 1975 by a scientist notassociated with the present inventors working in the field of disposablethermometry (who was attempting to develop a reversible thermometerthrough a color change of a dye by use of molten thermometer chemicalsinstead of solid thermometer chemicals) a curious phenomenom wasrevealed. By mixing ethyl red and bromothymol blue together in a"thermometer chemical", he found out that a "very obvious color change"took place when melting and freezing of the mixture occurred. When thechemical solidified, the color changed to yellow-orange. The reactionappeared to him to be completely reversible. Screening tests withavailable dyes and indicators apparently showed the scientist thatbromophenol blue and bromocresol purple could be substituted forbromothymol blue. Similar structures without the bromine atoms did notwork; e.g., thymol blue, cresol phthalein, thymol phthalein. Thescientist also apparently found that suitable structures for replacementof ethyl red included crystal violet, para rosaniline base, pararosaniline acetate, new fuchsin, basic function and 8-hydroxyquinoline.The memo stated that the 8-hydroxyquinoline, although not a dye orindicator, served as a substitute by allowing the bromo compound tochange from yellow to blue-green from solid to liquid form. Thescientist reported that the indicating compounds were then tried invarious solid solvent systems, and that the color change only took placein aromatic systems such as naphthalene, 2-ethoxybenzamide, thymol and2-naphthyl. Aliphatic compounds such as 2-chloroacetamide and sorbitoldid not exhibit color changes. The report concluded with a statementthat imidazole was too strongly basic to exhibit any change since theindicators went to the basic state and remained there.

An intercompany sale of thermometers with pinacyanol iodide/OCNB-OBNBwithin claim 1 of this invention was made on Sept. 30, 1977, forpurposes of research by an unincorporated division of assignee ofApplicants to Organon Technika B.V., a related company to said assignee.Sales by the assignee in the United States to the public commencedshortly after Jan. 1, 1978.

AN INVENTION

The present inventors learned of this abandoned attempt about eighteenmonths later than the date of the memorandum through atechnology-transfer agreement and amongst other attempts by differentmethods (use of metal complexes, different solutions of cations, etc.)to obtain an inexpensive disposable (and possibly reversible)thermometer, performed the identical experiments as perceived by readingthe short memorandum. The color change did not work for the desireddisposable thermometer applications in these experiments because (1) abroad melting point was experienced and, as the memorandum did notindicate in what proportion the components were to be mixed, (2) muchexperimentation had to be performed to adjust the ratios of the firstand second types of compounds mentioned above for any color change tooccur. Even after the present inventors found the correct ratios of"Group I" to "Group II" type materials relative to each other, the broadmelting range still presented a seemingly unsurmountable problem. Theunpublished memo above did not mention any phenomena of the "Group III"compounds listed below.

Surprisingly, when the Group I and Group II components were mixed in acertain ratio found by the inventors and were added to the composition(at a total weight of about 0.05%), and when the solvent(ortho-chloronitrobenzene and ortho-bromonitrobenzene) was employed in acomposition almost entirely free of nucleating agents (impurities,especially less than 0.1 weight percent), a sharp and narrow meltingrange (or "point") with a sharp color change was discovered for thecomposition, which at the same time exhibited the desired color changewith change in phases and a remarkable color stability in the liquidupon heating, presumably due to some type of undercooling effect, i.e.,upon withdrawal from the source of the temperature to be measured, thematerials were not readily susceptible to refreezing and colorreversibility. The exact mechanism for this sharp color change phenomenais unknown and only theories have been postulated.

THE PRESENT ART

German Patent Application No. 27,15,752 (published Oct. 27, 1977)discloses, inter alia, the use of an ionic reaction between the solventmixture (for example, n-octadecane/n-eicosane) upon melting to ionize apair of color producing reagents (for example methyl red and acid clay).More specifically, the color signal in No. 27,15,752 is developed byphysically separating two reactive components which are later united ata visually accessible site by the action of the flow of the liquid phaseof the temperature sensitive composition. The authors describe that thismay be accomplished by applying each reagent on separate sides of abibulum or by dissolving one reagent in the melting substance andapplying each reagent in the melting substance and applying the other tothe bibulum. The German reference is seen as no more pertinent than U.S.Pat. No. 3,712,141 (Chadha).

Suzuki et al. in U.S. Pat. No. 4,015,591 teaches the manufacture of acomposition of matter having thermal color responsive characteristics(adapted for effecting vanapuncture in the human body) and comprising anentantiotropic cholesteric liquid crystalline phase material, and atleast two oil-soluble dyes dissolved in the material in a total dyeconcentration of 0.01-1.0 weight percent of the composition and with thedyes together absorbing light of substantially all wave lengths withinthe range.

An application, filed on or about Apr. 13, 1978, Ser. No. 896,116,entitled "DYE IN CHEMICAL TEMPERATURE INDICATING DEVICE", and assignedto assignee of the present invention, describes an invention wherein acavity is filled with a solid mixture (preferablyortho-chloronitrobenzene/orthobromonitrobenzene (hereinafter OCNB/OBNB),including a dye which, although not changing color with change in phase,upon melting turns the color of a bibulum layer to the color of the dye.

Another application, filed on or about Apr. 13, 1978, Ser. No. 896,114,now U.S. Pat. No. 4,189,942 entitled "TEMPERATURE INDICATING DEVICEUSING A PRESSURE-SENSITIVE ADHESIVE SEAL", also assigned to the assigneeof the present invention, discloses the use of polyisobutylene (PIB) ora similar material having higher surface tension with respect to certainsolvents (OCNB/OBNB, for example) than conventional materials of theart, such as SURLYN®1652 (E.I. duPont deNemours & Company). Thisinvention can be employed in any system wherein the dye is in a mixturewith the solvent.

SUMMARY OF THE INVENTION

Novel and stable temperature indicating compositions are provided foruse in a number of different types of disposable thermometers formeasuring the temperature of human and other animal bodies, and forother temperature measurement applications in industry as well.Furthermore, the application of these novel chemical compositions arenot limited to use in clinical or industrial applications induced bytemperature changes, but may be extended to other indication ormeasuring systems in which the color change described can be used toindicate a liquid to solid or solid to liquid phase change in anon-polar solvent or weakly polar solvent induced by pressure,radiation, electromotive forces or other kinetic energy sources.

The constituents of the novel compositions of matter comprise:

(1) a solvent (I) consisting of a single substance or a mixture ofsubstances and adapted to change from a solid state at substantially apredetermined temperature to a liquid state and

(2) an indicator system (II) consisting of one or more substancesdifferent from (I), characterized in that:

(a) (II) is soluble in (I) when the latter is in the liquid phase, and

(b) (II) changes a color visible to the naked eye when (I) passes fromthe solid to the liquid phase or from the liquid to the solid phase.

The constituents of the novel compositions of matter substantially freeof impurities most preferably comprise (a) a suitable inert solvent(i.e., stable and in which Group I-III moieties are soluble, andgenerally aromatic hydrocarbons) adapted to change from a solid state atsubstantially a predetermined temperature to a liquid state, and (b) aneffective amount (generally about 0.005 to about 0.5 percent preferablyabout 0.025 to about 0.05 percent by weight) of (1) one or more GroupIII compounds (pinacyanol iodide, quinaldine red,1,1'-diethyl-2,2'-cyanine iodide, pinacyanol chloride, thionin,methylene blue, cresol red, chlorophenol red, neutral red iodide,neutral red chloride, crystal violet, acridin orange, toluidin blue O,Orasol Orange RLN™, Orasol Navy Blue™, Irgalith Red PR™, Fat Red BS™,Xylene Cyanol FF™, Rhodamine 6G™, Irgalith Magenta TCB™, Irgalith PinkTYNC™, Toluidin blue O™, Savinyl Green B™, Savinyl Blue RS™, purpurin,3,3'-diethylthiadicarbocyanine iodide, cryptocyanine, Dicyanine A™,Merocyanine 540™, 4-(P-ethoxyphenylazo)-m-phenylene diaminemonohydrochloride, Yellow Orange S™, Chrysoidin G™, fuchsin,aurintricarboxylic acid (ammonium salt), Victoria Blue R™, Pyronin G™,gallein Erythrosin Yellowish Blend™, chlorophenol blue, bromophenolblue, bromocresol purple, Coriphosphine O™, acriflavine, acridineorange, rhoduline violet, Alizarin cyanin 2R™, Alizarin Red S™,alcannin, Aurantia™, Direct Green G™, Fast Red Salt 3GL™, Fast Blue SaltBB™, Fast Garnet Salt GBC™, Carta Yellow G 180 o/o, Muroxide SavinylBlue GLS™, Irgalith Blue GLSM™, phthalocyaline, Di Amingreen B™,Alizarin Blue S™, Celliton Blue Extra™, Janus Green, dimethyl yellow,Fast Yellow, Methyl red sodium salt, Alizarin yellow R™, Eriochromeblack T™, Chromotrope 2R™, Ponceau 6R™, Brilliant Ponceau G/R/2R™,chromolan yellow, Sudan Red B™, Bismarck brown G™, Fat Black™, ResorcinBrown™, Benzofast pink 2BL™, Oil Red EGN™, Euroglaucine, Fuchsin NB™,parafuchsin, Patent Blue™, Irgalith Blue TNC™, Phloxin B™, fluoresceinsodium salt, Rhodamine B base™, Eosinscarlet, Eosin Yellowish™,Erythrosin extrabluish, 4,5-dibromo fluorescein, ethyleosin, Phloxine,Cyanovin B™, chlorocresol green, pinacyanol bromide,2-(p-dimethylaminostyryl)-1-1-ethyl pyridinium iodide, ethyl red,nigrosine, savinyl blue B™, Orasol Blue BLN™, Safranin O™, Azocarnun G™,Phenosafranine, Azocarmine BX™, Solophenyl Brilliant Blue BL™, Nile BlueA™, gallocyanine, gallanine blue, celestine blue, methylene green, AzureA/B/C™, Blue VIF Organol™, Alizarin, Nitrofast Green GSB™,quinalizarine, Oil Blue N™, Solvay purple, Ciba Blue™, Indigosynthetic™, Chromophtal Bordeaux RS™, acid Alizarin Red B™,5-Aminoflourescein, Rose Bengal™, Martius Yellow™, Chicago Blue 6B™,Alcian Blue 8GX, cresyl violet, 4,4'Bis(dimethylamino)benzylhdrol, ZincPthalocyanine, Sudan III™, Pyronin Y™, Toluylene Blue™, Cresyl Violetperchlorate, Mendola's Blue™, 3,3'-diethylthiadicarbocyanine iodide,Phosphine Dye™, Nitron™, Cresyl violet acetate, Ceres Orange R™,4-phenylazo-1-naphthyl-amine, 4-(4-Dimethylamino-1-naphthylazo-3-methoxybenzene sulfonic acid, Bindschedler's Green™, andp-(p-dimethylamino phenylazo) benzoic acid and neocyanine) or in thealternative, (2) a similarly small amount of one or more of a Group Ibody of compounds consisting of the halogenated sulfonphthaleins andorganic acids having a pK of less than about four, together with one ormore of a Group II body of compounds consisting of theaminotriphenylmethanes and their soluble salts, 8-hydroxyquinoline, andthe cyanines (with the proviso that if the Group II compounds consistsolely of one or more aminotriphenylmethanes or their soluble salts,then Group I must be selected from one or more of the group consistingof oxalic acid, suitable soluble sulfonic acids, the tetrahalogenatedsulfonphthaleins and the other known soluble organic acids having a pK₁of about 2 or less dissolved in the above-mentioned suitable solvents.Examples of Group I compounds suitable for use in this invention are oneor more of the group consisting of oxalic acid, maleic acid,dichloroacetic acid, trichloroacetic acid, naphthalene sulfonic acid,benzensulfonic acid, chloroanilic acid, bromophenol blue, bromothymolblue, chlorophenol red, bromochlorophenol blue, bromocresol green,3,4,5,6-tetrabromophenolsulfonphthalein, bromophenol red, chlorophenolblue, bromocresol purple, 2,4-dinitrobenzenesulphonic acid, andchlorocresol green. Examples of Group II compounds suitable for use inthis invention are ethyl red, crystal violet, pararosaniline,pararosaniline acetate, basic fuchsin, 8-hydroxyquinoline, ethyl violet,brilliant green, pinacyanol chloride, and3,3'-diethylthiodicarbocyanine. Preferable combinations of Group I andGroup II compounds when Group III compounds are not employed are: (1)bromophenol blue: basic fuchsin; (2) chlorophenol blue: ethyl red; (3)chlorophenol red: ethyl red; (4) bromophenol red: ethyl red; and ( 5)bromochlorophenol blue: brilliant green. If a Group III compound is notemployed, the weight ratio of the Group I to Group II compound is morethan or about 3 to 1. A Group III compound in an effective amount may beused alone or together with any small amount (preferably less than about0.5 percent) of Group I and/or Group II compound.

A most preferable solvent system for use in measuring temperatures inthe human clinical temperature range is that of ortho-bromonitrobenzeneand ortho-chloronitrobenzene (OBNB:OCNB) wherein the ratio ofortho-bromonitrobenze to ortho-chloronitrobenzene varies from about56.2:43.8 to about 96.0:4.0, which, when in use with approximately 0.05percent by weight of Group I-III compounds yields an accurate system formeasurement of temperatures from 96.0° F. to 105° F. The OBNB:OCNBsolvent system also allows the temperature to be measured within therange of 96° F. to 105° F. within 0.2° F. or 0.1° C.

The invention also contemplates a novel temperature-indicating devicecomprising (a) a flat or gradually curved heat-conducting carrier havingone or more regions defined therein, preferably cavities, to determine alike number of predetermined temperatures at temperatures separated by aconstant increment in a predetermined temperature range by means of alike number of different thermally-responsive compositions of matter,each cavity associated with one of the predetermined temperatures andeach substantially without impurities, (b) if the novel compositions ofour invention are not employed, an indicator means located at the bottomof each said cavities, (c) a transparent means in sealing engagementwith a carrier means above each cavity and overlying each of saidcavities to form an enclosure for each cavity between the walls of thecavity and the transparent means, and (d) one of said compositions ofmatter adapted to change from a solid to a liquid at substantially thepredetermined temperature associated with said cavity, and in addition,substantially filling the cavity except for a substantially sphericalvoid within said cavity and composition of matter. The novel temperatureindicator device does not contemplate the necessity of employing thenovel temperature-indicating compositions of matter, but can, in thealternative, employ the "classical" compositions of matter (compositionsother than our novel compositions which generally change from opaque totransparent with a corresponding change in phase at a predeterminedtemperature). On the other hand, if the novel compositions of matter areemployed, the indicator means in the novel temperature-indicating devicemay be eliminated. The invention contemplates use of the novel devicefor ordinary opaque thermometers where the entire backing material iscolored, or when a cover layer of bibulum paper is employed, or whennumerals are employed at the bottom of void spaces.

In one aspect, this invention contemplates providing thermally-sensitivecompositions which undergo a change of state, i.e., from solid toliquid, at precisely predetermined temperatures with a correspondingchange of color visible to the naked eye; such temperature-sensitivecompositions being solid solutions of certain organic compounds to behereinafter described.

In another aspect, the present invention is concerned with providingsolid solutions which undergo a change of state rapidly over a verynarrow temperature range, e.g., within an accuracy of 1/10° C., or inthe alternative, within an accuracy of 2/10° F., so that the solidsolutions may be employed for a measurement of temperature within apredetermined temperature range, for example, the clinical range of 96°F. to 105° F. or 35.5° C. to 40.4° C. An example of a device is a diskwith three void spaces containing three novel compositions melting atdifferent temperatures which might (a) be placed on a baby's abdomen todetect fever or (b) be placed on a person's forehead to detect a likefever. Such an example has obvious advantages in the detection ofmalignant hyperthermia; see Nerida M. Dilworth, "THE IMPORTANCE OFCHANGES IN BODY TEMPERATURE IN PAEDIATRIC SURGERY AND ANAESTHESIA",Anaesthesia and Intensive Care, Vol. 1, No. 6 (November 1973) 480 etseq.

Another aspect of this invention is directed to the use of an indicatingsystem associated with the novel compositions of matter so as to obtaina rapid visual indication of the change of state of such material, andhence, the temperature of the test subject.

Furthermore, another aspect of this invention is directed toward theprovision of novel compositions of matter which may be applied to otherindication or measuring systems other than temperature measuring systemssuch as those suggested or taught by our invention in which the colorchange described can be used to indicate a liquid-to-solid orsolid-to-liquid change, preferably in a nonpolar solvent or weakly polarsolvent induced by pressure, radiation, electromotive forces, or otherkinetic energy sources.

In yet another aspect, the invention is directed toward the provision ofa novel temperature-indicating device suitable as a disposablethermometer, in which each temperature-sensitive composition of matterused is substantially free of impurities so that said composition ofmatter upon complete melting has few nucleation sites and is notconducive to resolidification, i.e., the temperature-sensitivecomposition of matter has the property of stable undercooling and willremain liquid for at least several minutes up to several hours whensubjected to a surrounding temperature that is somewhat below thefreezing point of the composition.

And yet still another aspect, the present invention is directed towardthe provision of a novel temperature-indicating device (comprising aflat or gradually curved heat conducting carrier means with one or morecavities therein and a transparent means in sealing engagement with saidcarrier means above the cavity) for use of so-called "classical"temperature-sensitive materials, e.g., compositions of matter commonlyemployed in disposable thermometers which change from opaque to becometransparent upon a change in phase from solid to liquid, through the useof a substantially spherical void within said cavity containing thecomposition of matter determining the temperature to be indicated tomagnify the presence of an indicator layer at the bottom of said cavity.

Finally, while other aspects of our invention will become apparent fromthe detailed description thereof, infra, the overall object of ourinvention is to provide generally useful improvements in change-of-statethermometers.

The details of the invention pertaining to the noveltemperature-indicating device will become more evident from the detaileddescription to follow with reference to the appended drawings:

FIG. 1 depicts a liquidous curve of a solid solution orortho-chloronitrobenzene and ortho-bromonitrobenzene for the humanclinical range of temperatures. The bands defined by the dash lines inthis diagram, greatly exaggerated, represent the limit of accuracy oftemperature measurements of this invention, i.e., plus or minus 1/10° C.or approximately plus or minus 2/10° F. The band is shown insubstantially exaggerated width (forty or fifty magnitude) in order tofacilitate this illustration;

FIG. 2 is a partial plan view from the horizontal of a flat or graduallycurved novel heat-conducting carrier having a cavity defined therein,which cavity forms an enclosure for a temperature-sensitive "classical"composition of matter therein when such cavity is covered by atransparent cover sheet means in sealing engagement with the carriermeans overlying the heat-conducting carrier means and above the cavity;the figure also depicts a substantially spherical cavity inside thetemperature-sensitive composition of matter;

FIG. 3 is a vertical section taken along line 3--3 of FIG. 2; it is thepartial plan view of the cavity when taken from the overhead of thecavity of FIG. 2 when a painted material is at the bottom of said cavityin an indicator means;

FIG. 4 is a vertical section taken along line 4--4 of FIG. 2; it is apartial plan view taken from the overhead of the cavity of FIG. 2 when apainted material is magnified due to a spherical cavity in the"classical" composition, when said composition of matter has melted;

FIG. 5 is a partial overhead plan view of a thermometer over part of thehuman clinical range of temperatures embodying the principles of thisinvention in degrees Celsius;

FIG. 6 is a partial overhead plan view of a thermometer over the humanclinical temperature range embodying the principles of this inventionwhen in degrees Fahrenheit;

FIG. 7 is a view of a thermometer with 10° F. increments when using thenovel compositions of matter of this invention in a commercialapplication;

FIG. 8 is a plan view of a temperature-indicating device from thehorizontal (together with a plan view from the vertical of a label onsaid device) using the novel compositions of matter of this inventionfor indication of a temperature exceeding a predetermined safe limit.The details of the above figures will be discussed, infra;

FIG. 9 is a cut-away three-dimensional view from a skewed angle of athermometer comprising a heat-conducting carrier means with a grid ofcavities thereon, enclosed in a case so that only a handle of theheat-conducting carrier means protrudes;

FIG. 10 is another three-dimensional view from the same skewed angle asFIG. 9 of the thermometer when removed from the case of FIG. 9, exceptthat it reveals a clinical temperature scale from 96.0° F. to 104.8° F.in the form of a grid of cavities in the heat-conducting carrier means;

FIG. 11 is a partial plan horizontal view taken along line II--II inFIG. 10, revealing several cavities in the heat-conducting carriermeans, each surrounded by a transparent cover sheet means and a bottomtransparent bottom plate means;

FIG. 12 is a plan view of a flat temperature-indicating device from thevertical without the use of a case, comprising a heat-conducting carriermeans with a grid of cavities thereon; and

FIG. 13 is a plan horizontal view taken along line 13--13 in FIG. 12revealing the heat-conducting carrier means, cavities within,transparent cover sheet means, and a bottom plate means.

FIG. 14 is a plan view taken from the vertical of a transparent supportmember for a disposable clinical thermometer either of FIG. 10 or FIGS.12-13.

FIG. 15 is a plan view taken from the vertical of the transparentsupport member of FIG. 14, except in sealing engagement, with adisposable thermometer such as that shown in FIG. 10 with a Fahrenheitscale from 96.0 degrees Fahrenheit to 104.8 degrees Fahrenheit graduatedin 0.2 degrees Fahrenheit increments.

FIG. 16 is a plan view taken from the vertical of the transparentsupport member of FIG. 14, except in sealing engagement with adisposable thermometer, such as that shown in FIG. 10, but with aCentigrade scale from 35.5 degrees Centigrade to 40.4 degrees Centigradegraduated in 0.1 degrees Centigrade increments.

FIG. 17 is a partial plan view from the horizontal of a flat orgradually curved novel heat-conducting carrier having a cavity definedtherein, where a cover layer is bonded to a carrier layer by apressure-sensitive adhesive layer comprised of polyisobutylene (PIB).

FIG. 18 is a partial plan view from the horizontal like FIG. 17 exceptusing an additional layer of PIB adjacent to the lower edges of thecavity.

Throughout the Detailed Description below, the terms "novelthermally-responsive substance", "novel thermally-responsive material","novel temperature-indicating compositions of matter", "noveltemperature-sensitive solid solutions", "novel temperature-indicatingsolid solutions", and "novel solid solutions", or variations thereof,are used interchangeably to denote the same novel materials of ourinvention. Otherwise, the term "compositions of matter" or "classicalcompositions of matter" are used interchangeably to denote compoundswhich change only from being opaque to transparent with a correspondingchange from the solid to liquid state, or vice versa.

DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENT

1. Novel Compositions of Matter

It has now been discovered unexpectedly that certain organic compounds(to be described hereinafter) form novel solid solutions which undergo achange in state from solid to liquid at precise and predeterminedtemperatures with a corresponding change in color visible to the nakedeye, and likewise, from liquid solutions which undergo a change in statefrom liquid to solid at precise and predetermined temperatures with acorresponding change in color visible to the naked eye. The term "solidsolution" is well known and usually refers to a homogenous solution ofone solid in another. The novel solid solutions contemplated in thepresent invention are composed of two or more, preferably three or four,different organic compounds with varying proportions of at least twocompounds which form a solvent for the solution. Each novel solidsolution undergoes a rapid change of state at a precise andpredetermined temperature or substantially thereabouts. By a "change incolor visible to the naked eye" of a source we mean a change in thewavelength of luminous flux of light (from the source distributing orreflecting such energy in the region of the Electromagnetic Spectrumfrom about 3900 Angstrom units to about 7600 Angstrom units before orafter the change, or preferably both) visible to a person of normalvision and eyesight wherein the intensity of the luminous fluxsurrounding the source is more than or about 5 lumens per square foot(ft-c). In most instances, this change in the wavelength of luminousflux to the eye will be at least about 175 Angstroms, and preferably atleast about 500 Angstroms.

Preferably, when a small but effective amount (generally a weightfraction from about 0.005 to 0.2 weight percentum, and generally about0.05 weight percentum of the entire composition, but the optimum may bemore or less upon experimentation, depending on the Group I-IIIcompounds selected and the solvent selected, up until both phases appeardark, appear the same color, or the melting point becomes too broad forthe use desired-some latitude for experimentation is present here) ofone or more of Group III compounds: pinacyanol iodide,1,1'-diethyl-2,2'-cyanine iodide, quinaldine red, pinacyanol chloride,thionin, methylene blue, cresol red, chlorophenol red, neutral rediodide, neutral red chloride, crystal violet, acridin orange, OrasolOrange RLN™, Orasol Navy Blue™, Irgalith Red PR™, Fat Red BS™, XyleneCyanol FF™, Rhodamine B, Rhodamine 6G™, Irgalith Magenta TCB™, IrgalithPink TYNC™, Toluidin Blue O™, Savinyl Green B, Savinyl Blue RS™,purpurin, 3,3'-diethyl-thiadicarbocyanine iodide, cryptocyanine,Dicyanine A™, Merocyanine 540™, 4-(p-ethoxyphenylazo)-m-phenylenediamine monohydrochloride, Yellow Orange S™, Chrysoidin G™, fuchsin,aurintricarboxylic acid (ammonium salt), Victoria Blue R™, Pyronin G™,gallein, Erythrosin Yellowish Blend™, chlorophenol blue, bromophenolblue, bromocresol purple, Coriphosphine O™, acriflavine, acridineorange, rhoduline violet, Alizarin cyanin 2R™, Alizarin Red S™,alcannin, Aurantia™, Direct Green G™, Fast Red Salt 3GL™, Fast Blue SaltBB™, Fast Garnet Salt GBC™, Carta Yellow G 180 Murexid o/o, Savinyl BlueGLS™, Irgalith Blue GLSM™, phthalocyanine, Di Amingreen B™, AlizarinBlue S, Celliton Blue Extra™, neocyanine, Janus Green™, dimethyl yellow,Fast Yellow, Methyl red sodium salt, Alizarin yellow R™, Eriochromeblack T™, Chromotrope 2R™, Ponceau 6R™, Brilliant Ponceau G/R/2R™,chromolan yellow, Sudan Red B™, Bismarck brown G™, Fat Black™, ResorcinBrown™, Benzofast pink 2BL™, Oil Red EGN™, Euroglaucine, Fushsin NB™,parafuchsin, Patent Blue™, Irgalith Blue TNC™, Phloxin B™, fluoresceinsodium salt, Rhodamine B base™, Eosinscarlet, Eosin Yellowish™,Erythrosin extrabluish, 4.5-dibromofluorescein, ethyleosin, Phloxine™,Cyanovin B™, chlorocresol green, pinacyanol bromide,2-(p-dimethylaminostyryl)-1-ethyl pyridinium iodide, ethyl red,nigrosine, savinyl blue B™, Orasol Blue BLN™, Safranin O™, Azocarnun G™,Phenosafranine, Azocarmine BX™, Solophenyl Brilliant Blue BL™, Nile BlueA™, gallocyanine, gallamine blue, celestine blue, methylene green, AzureA/B/C™, Blue VIF™ Organol™, Alizarin Nitrofast Green GSB™,quinalizarine, Oil Blue N™, Solvay purple, Ciba Blue™, Indigosynthetic™, Chromophtal Bordeaux RS™, Acid Alizarin Red B™,5-Aminofluorescein, Rose Bengal™, Martius Yellow™, Chicago Blue 6B™,Alcian Blue 8GX™, cresyl violet, 4,4'-Bis(dimethylamino)benzylhdrol,Zinc Pthalocyanine, Sudan III™, Pyronin Y™, Toluylene Blue™, CresylViolet perchlorate, Mendola's Blue™, 3,3'-diethylthiadicarbocyanineiodide, Phosphine Dye™, Nitron™, cresyl violet acetate, Ceres Orange R™,4-phenylazo-1-naphtyl-amine,4-(4-Dimethylamino-1-naphtylazo-3-methoxybenzene sulfonic acid,Bindschedler's Green™, and p-(p-dimethylaminophenylazo)benzoic acid, orone of the other organic moieties to be described (one or more Group Icompounds with one or more Group II compounds) is combined with asuitable solvent, for example, a pure mixture ofortho-chloronitrobenzene and ortho-bromonitrobenzene for use in clinicalapplications, the temperature of the change of state of a number ofsolid solutions with a corresponding change in color may be accomplishedat approximately 1/10° C. or 2/10° F. intervals, i.e., a change of stateof one novel temperature-sensitive composition of matter at atemperature 1/10° C. or 1/5° F. different from the temperature of chancein state of another novel composition of matter in an adjacent regioncontaining another proportion of the same organic moieties inortho-chloronitrobenzene and ortho-bromonitrobenzene. Thus, for example,in human clinical applications where temperature measurements in therange of 96° F. to 105° F. (or from 35.5° C. to 40.5° C.) are usuallydesired, 45 to 50 different solid solutions (differing in theirpercentage compositions but otherwise made from the same two components)will provide all of the necessary temperature gradations at incrementsof 2/10° F., i.e., 96.0°, 96.2°, 96.4°, etc., up and including 104.8°F., or in the alternative, 35.5°, 35.6°, 35.7°, up and including 40.4°C. The solution of ortho-chloronitrobenzene and ortho-bromonitrobenzene,when the ortho-bromonitrobenzene varies from 56.2 weight percent to 96.0weight percent, provides an excellent starting mixture for determinationof temperatures in the human clinical temperature range. Usually theaddition of the Group I-III organic moieties (hereinafter sometimes"organic moieties") consisting of a small but effective percentage ofone or more of the aforesaid Group III compounds, or a combination ofone or more Group I compounds with one or more Group II compoundsaffects the temperature curve in FIG. 1 by only a small increment E orE', which is substantially constant along the entire curve. Regardlessof the solvent system selected for a given predetermined temperaturerange, it is necessary that the organic moieties selected for the colorchange constitute a small but effective amount of moieties, e.g., atleast that amount sufficient to provoke a color change visible to thenaked eye, and preferably up to a saturated solution of Group I-IIIorganic moieties, and most preferably about 0.005 to about 0.2 weightpercent of an inert, preferably aromatic solvent constituents,constituting the remaining balance of the mixture. The Group I-Group IIImoieties may in some instances exceed 0.2 weight percentum as long asthe melting point remains sharp and both phases are not so dark as toeliminate a color change visible to the naked eye. If too small anamount of organic moieties is employed, the colors and the color changeare too faint under weak light; if too large an amount is employed, thecolors are too dark and the color change is harder to visualize andthere is a possibility that the sharpness of the melting point will beaffected. It is also noted that the organic moieties and suitablesolvent to be described should be substantially free of impurities;generally, such impurities should be kept less than three tenths of onepercent of the entire composition. Supersaturated solutions are notpreferred for reasons to be enumerated below.

It must be emphasized from the outset that once a proposed solventsystem has been selected (consisting of one or more compounds) for thetemperature(s) to be determined, the compound(s) of the system must betested for the Group I-III moieties for stability (i.e., inertness) andGroup I-III moieties are soluble in the compound(s) of the solvent. Thismust be done by routine testing, within the skill of those in the art.Only after the solvent system compound(s) are shown to dissolve theGroup I-III moieties and be inert towards them, can such a solventsystem be suitable for our invention.

While sometimes under fortuitous circumstances the solvent system mayconsist of only one compound, in most instances (as those skilled in theart will appreciate) the temperature to be determined will not readilybe obtainable without mixing two or more organic compounds for thesolvent system. Hence, for a temperature-indicating device, two or morerelated organic compound constituents in the solvent are especiallyhelpful for measuring forty or more temperatures located at regularincrements.

It is apparent from the foregoing description that the selection of oneor more inert solvents towards the organic moieties for use in the novelcomposition of matter requires judicious and careful scrutiny, since notall organic compounds are useful for this purpose and many may falloutside a desired temperature range. A suitable solvent may be anysolvent which is inert towards the organic moieties and in which theorganic moieties are soluble while the solvent is in the liquid phase.In some instances, simple alcohols and other organic substances may besuitable (see Table 3) rather than aromatic compounds. The organiccompounds which are particularly adapted for the formations of solidsolutions which can serve a novel temperature-indicating composition inaccordance with the present invention are generally those which arearomatic weakly polar (e.g., compounds which are immiscible in water andhave a dielectric constant less than about 35) or moderately polararomatic organic compounds, as well as the requirements of organicmoiety solublity and inertness towards the organic moieties. Thus, ithas been discovered that weakly polar or moderately polar aromaticorganic compounds, which have analogous chemical structures (e.g.,analogs, homologs and optical isomers), have substantially the samemolecular volume or have similar crystalline structures (e.g.,isomorphous) are which form the novel solid solutions useful for thepurpose of this invention, are especially useful for solvent systemconstituents in preparing a grid of novel compositions of matter to beused in predetermined temperature range for the determination of atemperature falling within said range. In addition, it is preferablethat the solvent solutions have a linear or a substantially lineartemperature composition liquidous curve, particularly over the desiredtemperature range such as, for example, over the human clinicaltemperature range. Exemplary weakly polar or nonpolar aromatic solventsare ortho-chloronitrobenzene, ortho-bromonitrobenzene, naphthalene,2-ethoxybenzamide, 1-thymol, 2-naphthol, ortho-iodonitrobenzene,meta-iodonitrobenzene, para-iodonitrobenzene, para-chloronitrobenzene,meta-bromonitrobenzene, para-dibiomonitrobenzene and para-toluic acid.It must be emphasized, of course, that a suitable solvent useful for oneselection of organic moieties may not be useful for another, and that anoperable solvent at one temperature range may not work at a differentrange. It is recommended that for a given temperature to be measured,one may start his investigation for the appropriate temperature(s) to bedetermined a suitable solvent system selected from compounds from thefollowing:

(1) Moderately polar or weakly polar aromatic compounds, i.e., i.e.,compounds having a dielectric constant of less than about 35;

(2) water; or

(3) aromatic and aliphatic compounds other than (1)-(2) which aregermane to the temperatures to be determined, and which are "inert" tothe Group I-III dyes.

The constituents of the novel compositions of matter comprise:

(1) a solvent (I) consisting of a single substance or a mixture ofsubstances and adapted to change from a solid state at substantially apredetermined temperature to a liquid state and

(2) an indicator system (II) consisting of one or more substancesdifferent from (I), characterized in that

(a) (II) is soluble in (I) when the latter is in the liquid phase, and

(b) (II) changes color visible to the naked eye when (I) passes from thesolid to the liquid phase or from the liquid to the solid phase.

It is well within the range of knowledge of those skilled in the art tofind for a given temperature range to measured and for color changedesired (choosing from the various Group I-III compounds) a suitablesolvent, i.e., one which is in toward the Group I-III compounds and forwhich the latter a soluble in the liquid phase in said solvent.

The solid solutions made from ortho-chloronitrobenzene andortho-bromonitrobenzene have been found to be most preferable for use intemperature measurements in the clinical range within the aforesaidaccuracy. Of course, as it will be readily understood by those skilledin the art, any two or more aromatic solvents as defined above in whichthe organic moieties to be described below are soluble, stable andinert, may be employed for thermometers if adaptable to the temperaturerange to be tested, and if capable together of forming a homogenoussolid solution.

Preferably the novel composition of matter consists essentially of:

(A) a suitable solvent adapted to change from a solid state at apredetermined temperature to a liquid state, and

(B) an effective amount of one or more suitable organic moieties solublein said solvent in the liquid state and adapted to change the color ofthe composition visible to the naked eye upon the change of state of thesolvent at substantially the predetermined temperature and selected fromone or more of the group consisting of

(1) a group III body of single compounds consisting of the cyanine classof dyes, suitable dyes from the following classes: monoazo, diazo,triarylmethane, xanthene, sulphonephthalein, acridul, guinoline, azine,oxazine, thiazine, anthraquinone, indigold, and the following individualcompounds: Aurantia™, Orasol orange RLN™, Diamin green B™, Direct greenG™, Fast Red salt 3 GL™, Fast blue salt BB™, Fast Garnet salt GBC™,Carta Yellow G 180 o/o™, Murexide, Savinyl blue GLS, Irgalith blueGLSM™, Phthalocyanine and Alcannin,

(2) mixtures of:

(a) one or more organic acid compounds, having a pK of less than aboutfour, and

(3) mixtures of

(a) one or more organic acids having a pK of less than about 2 and

(b) one or more acid dyes or acid indicators

(4) mixtures of

(a) one or more organic acid compounds having a pK of less than about 4

and

(b) one or more members of the group I body of compounds,

(5) mixtures of

(a) one or more basic dyes or basic indicators and

(b) one or more members of the group I body of compounds,

(6) mixtures of

(a) one or more dyes having a molecular structure containing a lactonegroup, and

(b) one or more acids having a pK of about 8 to about 12.

The compounds mentioned in group III are classified according to theColour Index, 3rd Edition (1971), published by the Society of Dyers andColourists, Great Britain and Conn's Biological Stains (9th ed 1977).

Suitable monoazo dyes are: 4-(p-Ethoxyphenylazo)-m-phenylene-diaminemonohydrochloride, Orasol Navy Blue™, Organol Orange, Janus Green™,Irgalith red P4R, Dimethyl yellow, Fast Yellow, Methyl red sodium salt,Alizarin Yellow R™, Eriochrome Black T, Chromotrope 2R, Ponceau 6R,Yellow Orange S™, Brilliant Ponceau 5R™, Chrysolidine G™, Eriochromeblack A, Benzyl orange, Brilliant Ponceau G/R/2R™ and chromolan yellow.

Suitable disazo dyes are: Fat red BS™, Sudan Red B™, Bismarck Brown G™,Fat Black™, Resorcin Brown™, Benzofast Pink 2 BL™ and Oil Red EGN™.

Suitable triarylmethane dyes are: Methyl violet, Xylene cyanol FF™,Erioglaucine™, Fuchsin NB™, Fuchsin, Parafuchsin, Aurintricarboxylicacid ammonium salt, Patent Blue, Victoria blue R™, Crystal violet andIrgalith Blue TNC™.

Suitable xanthene dyes are: Phloxin B, Fluorescein sodium salt,Rhodamine B™, Rhodamine B Base, Rhodamine 6G™, Pyronin G, IrgalithMagenta TCB™, Irgalith pink TYNC™, Eosin Scarlet™, Eosin Yellowish,Erythrosin extra bluish™, 4'5'-Dibromofluorescein, Ethyl eosin, Gallein,Phloxine™, Erythrosin yellowish Blend™ and Cyanosin B™.

The suitable sulphonephthaleins are: cresol red, chlorophenol red,chlorophenol blue, bromophenol blue, bromocresol purple and chlorocresolgreen.

The suitable acridine dyes are: Corisphosphine 0™, Acriflavine andacridine orange.

The suitable quinoline dyes are: pinacyanol chloride, pinacyanolbromide, pinacyanol iodide, quinaldine red, cryptocyanine,1,1'-Diethyl-2,2'-cyanine iodide,2-(p-Dimethylaminostyryl)-1-ethyl-pyridinium iodide,3,3'-Diethylthiadicarbocyanine iodide, ethyl red, Dicyanine A,Merocyanine 540™ and Neocyanine™.

The suitable azine dyes are: Neutral red chloride, Neutral red iodide,Nigrosine™, Savinyl blue B™, Orasol blue BLn™, Safranin O™, AzocarminG™, Phenosafranine™, Azocarmine BX™ and Rhoduline violet.

The suitable oxazine dyes are: Solophenyl Brilliant Blue BL™, Nile blueA™, Gallocyanine™, Gallamine Blue™ and Celestine blue.

The suitable dyes are: Methylene blue, Thionin, Toluidine Blue O,Methylene Green and Azure A/B/C™.

The suitable anthraquinone dyes are: Savinyl Green B™, Savinyl Blue RS,D+C Green 6™, Blue VIF Organol™, Alizarin, Alizarin Cyanin 2R™, CellitonBlue Extra™, Alizarin Blue S™, Nitro Fast Green GSB, Alizarin red S,Chinalizarin, Oil blue N, Solvay purple™ and Purpurin™.

The suitable indigoid dyes are: Ciba Blue™, Indigo Synthetic™,Chromophtal Bordeaux RS™ and Thioindigo red.

Instead of one or more group I compounds, to be used in the novelcomposition of matter, mixtures can be employed.

The group of organic acidic compounds with a pK less than about fourgenerally consists of organic acids and/or the halogenatedsulfonphthaleins, which are soluble in the selected solvent, when thelatter is in the liquid state. Examples of these acids include oxalicacid, maleic acid, dichloroacetic acid, trichloroacetic acid,2-napthalene-sulphonic acid, chloroanilic acid, bromophenol blue,bromothymol blue, chlorophenol red, bromochlorophenol blue, bromocresolgreen, 3,4,5,6-tetrabromophenolsulphonephthalein, sulfonphthaleinbromophenol red, chlorocresol green, chlorophenol blue, bromocresolpurple and 2,4-dinitrobenzenesulphonic acid.

The group of basic dyes or basic indicators are generally theaminotriphenyl methanes, also known as the triaryl methanes, or theirsoluble salts, 8-hydroxyquinoline and the quinoline dyes, preferably thecyanines. Examples are: basic fuchsin, pinacyanol iodide, pinacyanolchloride, pinacyanol bromide,2-p-(dimethylaminostyryl)-1-ethyl-pyridinium iodide, crystal violet,cryptocyanine, dicyanine A, 3,3'-diethylthiacarbocyanine iodide,1,1'-diethyl-2,2'-cyanine iodide, ethyl red, quinaldine red, ethylviolet, brilliant green, pararosaniline, pararosaniline acetate,8-hydroxy-quinoline, 1-ethylpyridinium iodide and5-(p-dimethylaminobenzilidine) rhodanine.

Preferably the weight of the acid compounds is about three or more timesthe weight of the basic compounds.

The above-mentioned pK values refer to the pK values as measured inwater. Generally it is preferred that the pK of the acidic compound islower than the corresponding pK value of the basic compound. Preferablythe acid compounds have a pK value less than about four and the basiccompounds have a pK value less than about 5.

It should be noted that when the basic compound consists solely of oneor more aminotriphenylmethanes or their soluble salts, the acid compoundmust be selected from the group consisting of tetrahalogenatedsulphonphthaleins and the other organic acids having a pK of less thanabout 2.

Preferred combinations of acidic compounds having a pK less than about 4and basic dyes or basic indicators are bromophenol blue/basic fuchsin,chlorophenol blue/ethyl red and trichloroaceticacid/3,3'-diethylthiadicarbocyanine iodide.

Mixtures of one or more organic acids having a pK less than about 2 andone or more acid dyes or acid indicators, used in the novel compositionof matter, change color when the solvent passes from the solid into theliquid phase or reversed. In this combination the acid dyes used arepreferably halogenated sulfonphthaleins.

Mixtures of one or more organic dyes, having a molecular structurecontaining a lactone group and one or more acids having a pK of about 8to about 12, used in a solvent also change color when the solvent passesfrom the solid phase into the liquid phase or reversed. In thatcombination the preferred compounds are crystal violet lactone and oneor more of acids such as phenol, bisphenol A, pyrocathechol or 3nitrophenol.

The novel compositions of matter most preferably comprise (a) a suitableinert solvent as described above adapted to change from a solid state toa liquid state at substantially the predetermined temperature and (b)one or more organic moieties soluble in said solvent and adapted tochange color upon the change in state of the solvent at substantiallythe predetermined temperature when so dissolved, and selected from:

(1) one or more Group III compounds consisting of: pinacyanol iodide,quinaldine red, 1,1'-diethyl-2,2'-cyanine iodide, pinacyanol chloride,thionin, methylene blue, cresol red, chlorophenol red, neutral rediodide, neutral red chloride, crystal violet, acridin orange, toluidinblue O, Orasol Orange RLN™, Orasol Navy Blue™, Irgalith Red PR™, Fat RedBS™, methyl violet, Xylene Cyanol FF™, Rhodamine B™, Rhodamine 6G™,Irgalith Magenta TCB™, Irgalith Pink TYNC™, Toluidin Blue O™, SavinylGreen B™, Savinyl Blue RS™, purpurin, 3,3'-diethylthiadicarbocyanineiodide, cryptocyanine, Dicyanine A, merocyanine 540,4-(p-ethoxyphenylazo)-m-phenylene diamine monohydrochloride, YellowOrange S™, Chrysoidan G™, fuchsin, Aurintricarboxylic acid (ammoniumsalt), Victoria Blue R™, Pyronin G™, gallein phloxine, Erythrosin YellowBlend™, chlorophenol blue, bromophenol blue, bromocresol purple,Coriphosphine O™, acriflavine, acridine orange, rhoduline violet,Alizarin cyanin 2R™, Alizarin Red S™, alcannin, Aurantia, Direct GreenG™, Fast Red Salt 3GL™, Fast Blue Salt BB™, Fast Garnet Salt GBC™, CartaYellow G 180 o/o™, murexide, Savinyl Blue GLS™, Irgalith Blue GLSM™,phthalocyanine, Di Amingreen B™, Alizarin Blue S™, Celliton Blue Extra,neocyanine, Janus Green™, dimethyl yellow, Fast Yellow™, methyl redsodium salt, Alizarin yellow R™, Eriochrome black T™, Chromotrope 2R™,Ponceau 6R™, Brilliant Ponceau G/R/2R™, Chromolan yellow, Sudan Red B™,Bismarck brown G™, Fat Black™, Resorcin Brown™, Benzofast pink 2BL™, OilRed EGN™, Euroglaucine, Fushsin NB™, parafuchsin, Patent Blue™, IrgalithBlue TNC™, Phloxin B™, fluorescein sodium salt, Rhodamine B base™,Eosinscarlet, Eosin Yellowish™, Erythrosin extra bluish, 4',5-dibromofluorescein, ethyleosin, Phloxine™, Cyanovin B™, chlorocresol green,pinacyanol bromide, 2-(p-dimethylaminostyryl)-1-1-ethyl pyridiniumiodide, ethyl red, neutral red, iodide, nigrosine, Savinyl Blue B™,Orasol Blue BLN™, Safranin O™, Azocarnun G™, Phenosafranine, AzocarmineBX™, Solophenyl Brilliant Blue BL™, Nile Blue A™, gallocyanine,gallamine blue, celestine blue, methylene green, Azure A/B/C™, Blue VIFOrganol™, Alizarin, Nitrofast Green GSB™, quinalizarine, Oil blue N™,Solvay Purple™, Ciba Blue™, Indigo synthetic™, Chromophtal Bordeaux RS™,Thiorifolex™, Acid Alizarin Red B™, 5-aminoflourescein, Rose Bengel™,Martius Yellow™, Chicago Blue 6B™, Alcian Blue 86X™, cresyl violet,4,4'Bis(dimethylamino) benzylhydrol, Zinc Pthalocyanine, Sudan III™,Pyronin Y™, Toluylene Blue™, cresyl violet perchlorate, Mendola's Blue™,3,3'-diethylthiadicarbocyanine iodide, Phosphine Dye™, Nitron™, cresylviolet acetate, ceres orange R™, 4-phenylazo-1-naphtyl-amine,4-(4-Dimethylamino-1-naptylazo)-3-methoxybenzene sulfonic acid,Bindschedler's Green™, and p-(p-dimethylaminophenylazo)benzoic acid(hereinafterwards referred to as the Group III compounds or or Group IIIorganic moieties), or

(2) a binary mixture of:

(A) one or more of a Group I body of compounds (hereinafterwardsreferred to as the Group I compounds) consisting of (a) the organicacids, which when inserted in the solvent system at conditions otherthan supersaturation will yield a color change visible to the naked eye,and also have a pK of less than about four and (b) the halogenatedsulfonphthaleins; and

(B) one or more of a Group II body of compounds (hereinafterwardsreferred to as the Group II compounds) consisting of theaminotriphenylmethanes and their soluble salts, 8-hydroxyquinoline, andthe cyanines,

with the proviso that if no Group III compound is present and if theGroup II compounds consist solely of one or more aminotriphenylmethanesor their soluble salts, then the Group I compound must be selected fromone or more of the group consisting of oxalic acid, suitable sulfonicacids and the tetrahalogenated sulfonphthaleins, and other organic acidshaving a pK₁ of about or less than 2.

Of course, the primary application of the instant invention is where thechange in state of the novel composition of matter is induced bytemperature forces for use in a temperature-indicating device. By"suitable sulfonic acids" we mean sulfonic acids soluble in the selectedsolvent; these may be, for example, benzene sulfonic acid, naphthalenesulfonic acid, toluene sulfonic acid, anthracene sulfonic acid, etc.,depending on the solvent.

One of the requisites of our invention is that each novel compositionhave the property of supercooling. We require that if and only if agiven composition reaches one hundred percent liquid after melting, willthat liquid remain liquid for more than several seconds when withdrawnfrom the source whose temperature is to be measured; less than onehundred percent melting will cause the composition to returninstantaneously to its solid state when the composition is withdrawnfrom the above-mentioned source. It is only by these means that acommercially useful composition for disposable thermometry canmeasurably advance the state of the art. We have found, surprisingly,that the best method of obtaining the "undercooling property" in each ofour novel compositions of matter is to render them substantially free ofimpurities to the extent stated below, although doubtlessly theundercooling effect can be made through different alternativemechanisms--for example, several organic solvents exist for the GroupI-III compounds (high molecular weight aliphatic alcohols) which becomesuddenly very viscous in their liquid state close to solidification, sothat they possess the undercooling property despite the presence of someimpurities, i.e., these compounds form glasses. Hence, this limitednumber of solvents are equivalent to the general solvents used in ourinvention which are substantially free from impurities.

The novel composition should therefore be substantially free fromimpurities, i.e., they should have few impurities that are soluble inthe novel compositions of matter (generally which may not exceed about0.3 percent), and have few solid foreign substances that react with thenovel composition or that might induce instantaneous resolidificationafter melting (i.e. immediate reversibility). Impurities are defined asany substance other than the Group I-III moieties and the suitablesolvents and may be soluble or insoluble, but exclude suitablenucleating agents used in an effective amount. Generally, if thesesoluble substances are less than about 0.3 weight percent of the entirecomposition, the desired undercooling effect will not be altered. Toogreat an amount of soluble impurity results in a broad melting point fora given composition or separation of the Group I-Group III moiety(s)from the suitable solvent. On the other hand, a very small amount of asoluble impurity inert to the composition (generally less than about 0.3percent) may act in the same desirous manner as the recited insolublesuitable nucleating agents. If the weight percentum of these solublesubstances is less than about 0.1 weight percent, the desiredundercooling effect will almost always be observed. It must be notedthat any insoluble foreign substance chemically inert to the combinationof the Group I-Group III moieties and the suitable solvent may beutilized as a suitable nucleating agent so long as the foreign substancedoes not induce instantaneous resolidificaton at temperatures just belowthe melting point. Examples of suitable insoluble nucleating agents aregiven below (most preferably talc) and are employed in an effectiveamount to promote resolidification of the novel composition at apredetermined gradient below the melting point so long as absorption ofthe Group I-Group III moieties by the nucleating agent is within anacceptable range. Too great an amount of nucleating agent results inunacceptable absorption of the Group I-III moieties by the nucleatingagent, and removal of the otherwise occurring change in color visible tothe naked eye. Generally, the upper limit of suitable insolublenucleating agent varies from 0.1 to 10 weight percent of thecomposition, depending upon the suitable nucleating agent, suitablesolvent, and Group I-III moiety(s) selected. For example, in anOCNB-OBNB system with 0.05 weight percent pinacyanol iodide, aneffective amount of talc (as a suitable nucleating agent) is preferablyfrom about 0.01 to about 1.5 weight percent of the entire composition(and even up to in some circumstances ten percent and higher), dependingon the gradient between melting point and recrystallization temperatureselected. We have found 0.1 percent to be most preferable and that highconcentrations may affect the color change for a particular system. Iftoo great an amount of talc is used (over about two percent), in apinacyanol iodide/OCNB-OBNB system, the composition is always bluewhether in a liquid or solid state. Hence, as will be recognized by oneskilled in the art, a suitable nucleating agent may consist of (1) anyinsoluble foreign substance inert to the Group I-III moieties and thesuitable solvents, so long as the foreign substance does not induceinstantaneous solidification, or (2) a substance soluble in and inert tothe composition, but limited to less than about 0.3 weight percent ofthe composition.

An interesting phenomena exhibited by the novel compositions isillustrated by the example of a composition essentially consisting ofpinacyanol iodide (at 0.035 weight percent) inortho-bromonitrobenzene:ortho-chloronitrobenzene (75:25) solvent. In theliquid phase this composition is blue, and in the solid phase appearsrose/tan. However, if the composition is chilled to a very lowtemperature at a very high rate of cooling initially, the color of thesolid appears purple. As the composition is allowed to warm to roomtemperature, the color changes from purple to rose/tan, requiring about3-5 minutes for the color to become rose/tan. (similar phenomena haebeen observed with other novel compositions containing other Group IIImoieties or other Group I plus Group II combinations).

During solidification of the composition the chlorophenol red isconcentrated in the remaining liquid part of the solvent. When thesolidification has been completed the solid has a nice red color.Microscopic investigation of the solid composition shows that thechlorophenol red particles have been substantially separated from thesolvent crystals. In our opinion the intra-molecular rearrangement of asultone group, when the chlorophenol red is dissolved in the liquidsolvent, into a quinone structure, when the chlorophenol red isseparated, is responsible for this color change.

When the indicator system comprises more than one component, the colorchange often will be caused by chemical reactions between the indicatorcompounds.

Why pinacyanol iodide changes its color upon being separated from thesolvent compounds is not fully understood at this time.

The color change may be caused by an intermolecular interaction betweenthe pinacyanol ion and the counter ion. It is most likely that thepinacyanol iodide crystals, being formed upon separation of the solvent,consist of a stack structure with columns of positive dye ions andnegative counter ions. Such a structure might give raise to a drasticchange in resonance as compared with the unpertubed state of dissolvedpinacyanol iodide.

Another example of an especially preferred group I compound ischlorophenol red at a concentration of about 0.05 percent by mass. Whendissolved in a solvent such as OCNB/OBNB, dibenzofurane, para-toluicacid and other halogen nitrobenzenes, the liquid composition has ayellow color.

As enumerated above, in the absence of one or more Group III compoundsto be used for the organic moieties in the solvent system, one or moreof a Group I body of compounds must be employed together with one ormore of a Group II body of compounds. The Group I body of compoundsgenerally consist of (a) the organic acids, which when inserted in thesolvent system (at conditions other than supersaturation) will yield acolor change visible to the naked eye, and have a pK of less than aboutfour, and (b) the halogenated sulfonphthaleins which are soluble in theselected weakly polar or nonpolar aromatic solvent described above.Preferably, the Group I compound has a pK of between zero and three, andmost preferably between about zero and about two. Examples of this GroupI body of compounds include oxalic acid, naphthalenesulfonic acid,trichloroacetic acid, bromophenol blue, bromothymol blue, chlorophenolred, bromochloropehnol blue, bromocresol green, 3,4,5,6-tetrabromophenolsulfonphthalein, bromophenol red, and chlorocresol green. Somecompounds, such as maleic acid, will work if soluble in thepredetermined solvent system employed if the correct Group II compoundis chosen.

These first groups of compounds, which are generally the halogenatedsulfonphthaleins, are derivatives of the sulfonphthaleins, to wit,phenol blue, cresol red and phenol red. It may be observed that thehalogenated sulfonphthaleins are different from the basic orunsubstituted sulfonphthaleins in the following ways: first, theunsubstituted compounds are diprotic acid/base indicators, each havingpK values of (1) a pK₁ of about 2 and (2) a pK₂ of about 7 to about 9.The halogenated derivatives show only one pK which is much lower thanthe pK₂ of the unsubstituted sulfonphthalein. Because there are halogensubstituents on the suifonphthalein molecule, it is our belief (while wedo not limit the invention to the validity of our theory) that the pKvalue is reduced and the acid strength of the Group I is increased. As aconsequence of this, the halogenated derivatives will respond incombination with one or more of the Group II compounds enumerated belowto produce the color reaction. For example, in a OCNB-OBNB solventsystem and in combination with basic fuchsin (a Group II material),bromochlorophenol blue (a Group I material) gives a green color in thesolid phase and a strikingly red color in the liquid phase. This is verysimilar to the color found when the bromophenol blue (a Group Icompound) is combined with basic fuchsin in the sameortho-chloronitrobenzene:ortho-bromonitrobenzene solvent system.

The Group II compounds, which are generally the aminotriphenylmethanes,their soluble salts, 8-hydroxyquinoline, and the cyanines, act in ouropinion as constituents which perform a "dye" function. Of course, asindicated by the disclosure above, a Group I compound may also act as a"dye" function. Examples of Group II compounds include ethyl red,crystal violet, pararosaniline (or "para Rosaniline Base"),pararosaniline acetate (or "para Rosaniline acetate"), basic fuchsin,8-hydroxyquinoline, ethyl violet, brilliant green, pinacyanol chloride,and 3,3-diethylthiodicarbocyanine iodide. The Group I compounds arepreferably selected from the group consisting of bromophenol blue,bromochlorophenol blue, and bromothymol blue. One will notice that thesecond group of compounds generally consist of dyes which have basicnitrogen groups either as substituent amines or in heterocyclic rings.In general, the addition of one or more of the first group of compoundsalong with the second group of compounds to a solution of the previouslydescribed nonpolar or weakly polar aromatic solvent(s) such asortho-chloronitrobenzene and ortho-bromonitrobenzene solutions willprovide a color difference between the solid and liquid phases of thearomatic solvent. It is preferred that the total weight of the Group Iand Group II compounds be about 0.025 to about 0.05 total weight percentof the entire weight of the novel compositions of matter. It is advisedthat the melting point of the Group III or Group I and Group II moietiesbe more than the melting point of the solvent system. It is preferredthat the melting point of each of the Group I and Group II constituentsbe substantially more than the melting point of the solvent systemselected, and it is much preferred that these Group I and Group IIcompounds melt at more than sixty degrees above the melting point of thesolvent system. A basic requirement is that at least one of the Group Iand Group II compounds reflects or absorbs light in the visible area ofthe spectrum on or below the melting point of the solvent system or, inthe alternative, on or above the melting point of the solvent system, orboth, in different colors so that a change in color is visible to thenaked eye. It is also preferred that the Group I compounds weigh threeor more times the weight of the Group II compounds. While 0.05 weightpercent of the total of the Group I and Group II compounds or Group IIIcompound(s) is most preferred, any effective amount from the smallestfor which the change in color is visible to the naked eye upon change inphases is satisfactory, and certainly no more than the solubility limitsof the Group I and Group II compounds (or Group III compound(s)) in thesolvent system at the melting point of the solvent system. Too great anamount of Group I-III organic moieties renders the compositions obtaineddarker than necessary so that the color change is harder to detect;likewise, the melting point might also be affected. A supersaturatedsolution of Group I and Group II compounds (or Group III compound(s)) inthe solvent system, is not preferred, since Group I-III compounds aresubstantially more expensive than the solvent system constituents and anexcess of them will be extravagant. Any pressure may be employed inmaking or in using the novel composition(s) of matter in atemperature-indicating device so long as the solvent does not generate asubstantial vapor in the application for the composition. If a Group IIIcompound is not employed, it is preferred that the Group I compound havea lesser pK₁ and pK₂ value than the corresponding pK values of the GroupII compound. Preferably, the Group II compound should have a pK₁ valueof less than about 5, and the Group I compound should have a pK₁ of lessthan about 4.

As it will be appreciated by those skilled in the art, it is possiblewith the disclosure given above to combine almost any Group I compoundof indicated pK, which is soluble in the solvent system selected, (asolvent system of ortho-bromonitrobenzene: ortho-chloronitrobenzene, forexample) and a complementary acid base material from Group II andgenerate practically any desired change in color. The considerations forthose skilled in the art will be (1) the selection of Group III and/orGroup I and Group II compounds(s) which yield a satisfactory change inpredetermined colors; (2) that these compounds are soluble in thesolvent system in the liquid state; (3) that the solvent system beproperly determined for the temperature range desired; (4) that theGroup I and/or Group II compounds (or Group III compounds) be soluble inthe desired system, and (5) if pertinent, that one compound of the GroupI compounds react as a strong acid against one or more of the Group IIcompounds in the solvent system.

As it will be recognized by those skilled in the art, one may employcombinations of more than one Group III moiety, or a combination of aGroup III moiety and a Group I moiety, or a combination of a Group IImoiety and Group III moiety, or more than one Group I moiety with morethan one Group II moiety to obtain color shifts generally not found in asingle system, e.g., a mixture of pinacyanol iodide and quinaldine red(two Group III compounds) yields a tan solid and deep dark purpleliquid. There are some instances where two Group I compounds may beoperable where one acts as an acid relative to the other e.g., (1)naphthalene-sulfonic acid and one or more of (2) bromochlorophenol blue,chlorophenol blue, or bromocresol purple.

We have discovered that, as an alternative of using one or more of theGroup II compounds with one or more of the Group I compounds, one mayselect one of the aforesaid Group III compounds with (or preferably) inplace of a combination of one or more Group I compounds and one or moreGroup II compounds. A caveat and proviso must be stated: in absence of aGroup III compound one must employ one or more Group I compounds withone or more Group II compounds; if the Group II compounds consist solelyof one or more aminotriphenylmethanes or their soluble salts, then theGroup I compound must be from one or more of the group consisting ofoxalic acid, suitable sulfonic acids, tetrahalogenated sulfonphthaleins,and other soluble strong organic acids having a pK₁ of about or lessthan 2.

Without affecting the scope of the invention set out in the appendedclaims, what we believe to be a true mechanism for the color changeindicated above for organic moieties involving one or more Group Icompounds and one or more Group II compounds without the presence of aGroup II compound, and as will be more fully explained below, is the"reacting" of one or another of the compounds of one Group with anothercompound in another Group in acid/base reactions. This point is furtherverified by our finding that basic fuchsin (a Group II compound) incombination with naphthalenesulfonic acid (a Group I compound) dissolvedin an ortho-chloronitrobenzene:ortho-bromonitrobenzene (OCNB/OBNB)solution formed a purple color in the liquid phase and a yellow-to-greencolor in the solid phase, depending on the relative concentration of theGroup I compound in the novel composition of matter.

More specifically, one possible theory for the Group I-Group IIselection is that (1) the organic moieties are soluble in the liquidsolvent producing a color, but are less soluble in the solid solvent(i.e., do not form solid solutions). During crystallization of thesolvent, the compounds are concentrated. Again, according to thistheory, the Group I compound is an acid, which when concentratedprotonates or reacts in a neutralization reaction to cause the Group IIcompound to change from a color characteristic of a base form to a colorcharacteristic of an acid form of the compound. In this theory, simpleacids (e.g., nephthalene sulfonic acid, trichloroacetic acid) and acidicdyes (e.g., halogenated sulfonpthalein bromphencol blue) are bothconsidered to be acids.

Further, in a OCNB/OBNB system not employing oxalic acid which utilizesGroup I and Group II compound for example, bromochlorophenol blue andquinaldine red, a unique color change was obtained as follows: in theliquid phase, the bromochlorophenol blue (Group I) takes a proton fromthe quinaldine red, so that the quinaldine red takes on itscharacteristic basic red color (which is characteristic of the lattercompound dye between a pH of 2 and 13); on the other hand, in the solidphase, the bromochlorophenol blue protonates the quinaldine red and isyellow, at the same time quinaldine red is in its acid form and iscolorless. Hence, the solid phase is colored by the Group I dye in itsyellow form. Thus, the color of the liquid solution was red. Also, in anovel OCNB/OBNB composition employing a Group I and Group II compound,and with bromophenol blue as the Group I compound, and ethyl red as theGroup II compound in its acid form having no color whatsoever in thesolid phase of the solvent. Thus, the solid took on the yellowcoloration of the bromphenol blue. On the other hand, in the liquidform, the bromophenol blue is diluted in the solvent and the ethyl redbecomes the red color characteristic of the dye at a higher pH.

Another example of a Group I compound and a Group II compound isbromophenol blue and basic fuchsin. In the solid form, the basic fuchsinbehaved as if it were at a very low pH and was in a form which has agreen color between its pK₁ and pK₂. This green color of basic fuchsinat very low pH is a little known fact, but can easily be demonstrated inany laboratory with common reagents. In the liquid form, however, thebromophenol blue is yellow. The basic fuchsin was not in its first acidform and became red. Thus, the color of the liquid was red. With thisdisclosure, one skilled in the art will more appreciate the results tobe enumerated below in Examples 1-5 and in Table II.

As will be appreciated by those in the art, generally the color of theliquid is the same or similar to the color of the Group II compound orGroup III compound when dissolved in the liquid phase of most of thesuitable solvents employed.

Similarly, crystal violet, which is a pH indicator having a pK₁ ofapproximately 1, forms, in combination with oxalic acid and dissolvedinthe OCNB/OBNB solution, a blue liquid and a yellow solid.

We have also found as well that (1) quinaldine red (a Group IIIcompound) which has a pK₁ of approximately 1.6; (2) ethyl violet, whichhas a pK₁ of about 1.2; and (3) brilliant green, which has a pK₁ ofabout 1.4, all react in solutions with naphthalenesulfonic acid to formdifferent colored solid, then liquid, phases.

As as alternative to the above for Group I-Group II combinations, whenthe Group I material is other than a simple acid, and is a "dye"compound (such as bromophenol blue), in addition to the Group I'sbehavior as an acid, there may be formed in the composition aggregates,mixed polymers, and the like, which cause what is referred to in theliterature as "metachromism" or "metachromacy". "Metachromacy" is thatproperty of a substance which is expressed as a change in color(according to the wavelength of the light in which it is viewed) due toan outside force. "Metachromacy" is mainly attributed to that colorchange henomena when a dye is brought together with certain "tissue"molecules (macromolecules, e.g., solid materials such as heparin,polysaccharides). Certain organic dyestuffs, however, are characterizedby different colors when dissolved in inert solvents, which is describedas "solvatochromism". See HACKS'S CHEMICAL DICTIONARY 421 (4th ed.1969). The literature is full of articles attempting to give someexplanation of metachromacy (and "solvatochromism") apparently caused byincreasing dye concentration in the liquid phase, adding salts, orlowering the dielectric constant of the solvent from medium to lowvalues. Thus the literature speaks of salt-induced metachromism(increase in the concentration of salt), dye-induced metachromism(increase in concentration of dye) and dielectric-induced metachromism(decrease in the dielectric constant of the medium). The concept ofmetachromacy in the art was studied as a theory (definition), generallywith little practical application other than the coloring of tissue. Seethe classic article by R. B. McKay and P. J. Hillson, "MetachromaticBehavior of Dyes in Solution", 61 TRANS. FARADAY SOC. 1800-1810 (1965);also such as C. Guhaniyogi and Groja M. Mandal, "Studies onIntramolecular Association of Salt Groups in Polymers Following theirBinding with a Metachromatic Dye", 175 DIE MAKROMOLEKULARE CHEMIE823-831 (1974); Eryl D. Owen, et al., "Metachromic Interactions BetweenAzo and Triphenylmethane Dyes in Aqueous Solution", 25 J. APP. CHEM.BIOTECHNOL 211-219 (1975); M. K. Pal and Manju Chaduri, "CondutometricTitrations of Anionic Polyelectrolytes with Metachromatic Dyes andEffects of Organic Solvents", 133 DIE MAKROMOLEKULARE CHEMIE 151-160(1970); Ger. Pat. 2,327,723 (1973) to Pilot Ink Co.; A. Van Dormael,"Solvatochromism, Tautochromism, and Metachromism", 31 INDUSTRIECHIMIQUE BELGE 1-9 (No. 1, 1966); G. Scheibe, "Uber Metachromasie" 5PALETTE 28-34 (1970); R. B. McKay and P. J. Hillson, "MetachromaticBehavior of Dyes in Solvents of High Dielectric Constant: the Anomoly ofWater", 63 TRANS. FARADAY SOC. 777-781 (1967); a fascinating study byMedini Kanta Pal and Maxwell Schubert, "Simple and CompoundMetachromasia", 67 J. PHYS. CHEM. 1821 et seq (1963); M. K. Pal andSudhir Kumar Ash, "Metachromasia of Basic Dyes Induced by MercuricChloride II", 78 J. PHYS. CHEM. 536-540 (No. 5, 1974); Yamaokak et al.,"Diffuse reflectance Spectra of Metachromatic Dyes-Existence of a LongWavelength Band in Solid States", 78 J. PHYS. CHEM. 1040 (No. 10, 1974);CONN'S BIOLOGICAL STAINS 2-58 (9th ed. 1977); von F. Feichtmayr, et al."Einfluss der Dielectric Eigenschaften von Losungsmitteln and Substratenauf die Lichtabsorption and die Photochemische Verhatten vonKationischen Farbstoffen" (Losurgsmittel) OPTISCHE ANZEGUNG ORGANISCHESYSTEME VERLAG CHEMIE 1966 (West Germany) 357-374 (1964(?)); L.Micharelis and S. Granick, "Metachromasy of Basic Dyestuffs", 67 JACS1212 (1945); and P. J. Hillson and R. B. McKay "Metachromasy" 210 NATURE296-297 (1966); Paddy, J. F. METACHROMASY OF DYES IN SOLUTION, CHEM MOL.BIOL. INTERCELL. MATRIX ADVAN. STUDY INST. 1969: 1007-1031 (England).See also Japanese specifications Nos. 47-34735 and 50-105555.

Indeed, it would appear from the combined definition of Hackh andHillson/McKay that the phenomena of our invention may not fall withinthe definition of "metachromacy" (or even solvatochromacy) let alonerelying on metachromacy as a complete "mechanism" for understanding thephenomena of our invention.

Perhaps the closest article with a description of similar phenomena(components dissolved in a solvent changing color upon change in phasesis P. R. Hammond and L. A. Buckardt, "Electron Acceptor-Electron DonorInteractions. XV. Examination of Some Weak Charge-Transfer Interactionsand the Phenomenon of Thermachromism in these Systems", 74 J. PHYS.CHEM. 639 (No. 3, 1970). A number of pairs of non-dye donors andacceptors are listed at page 642 in solvents such as dichloromethane,cyclohexane, and n-hexane. "Thermochromasy" is the change in color of acomposition due to a change in temperature. See also Japanese patentapplications Nos. 75-105,554; 75,105,555; 75,107,040 by NorikayaNakasuji, et al (1975). Even Hammond/Burkardt, however, fail to give anyexplanation as far as single compounds (such as those in Group III)which exhibit the novel phenomena of our invention.

Perhaps one theory that night explain the latter phenomena observed isthat the Group III compound is soluble in the liquid solvent producing acolor, but has lower solubility in the solid phse of the solvent than inthe liquid phase (i.e., does not form a solid solution with thesolvent). During crystallizaton of the solvent, the dye is concentratedin the remaining liquid, and the concentration increases until the dyeand solvent have crystallized. The dye at the higher concentration or inits crystalline form exhibits "metachromatic-type" behavior, thusproducing a change in the color of the solid solvent/dye mass. Somesupport of this theory exists by way of microscopic evaluation ofpinacyanol iodide in an OCNB/OBNB solvent, wherein out of the blueliquid solution numerous light rose/light brown particles appear uponfreezing of the composition. As shown under the microscope, thecomposition of these particles may be of only dye, but they may as wellcomprise solvent dissolved in dye crystals.

Still another, yet unexplored, possible explanation of the phenomena ofour invention may exist in a so-called "heat dependent chemicaloscillating reaction", similar to the time dependent chemicaloscillating reactions familiar to those in the art (for examples of thelatter, see G. Nicolis and J. Portnow, "Chemical Oscillations", 73CHEMICAL REVIEWS (No. 4) 367-383 (1973). Hans Degn, "OscillatingChemical Reactions in Homogenous Phase", J. CHEM. EDUCATION 302 (May1972); R. J. Feld, "A Reaction Periodic In Time and Space", J. CHEM.EDUCATION 308 (May 1972); John F. Lefelhoiz, "The Color Blind TrafficLight", J. CHEM. EDUCATION 312 (May 1972); K. R. Sharma, et al,"Oscillations in Chemical Systems. VII. Effects of Light and of Oxygenon the Bray-Liebhof-sky Reaction", 97 J. AMER. CHEM. SOCIETY (No. 1) at202 (Jan. 8, 1975); Steven S. Jacobs and Irving R. Epstein, "Effects ofChloride Ion on Oscillations in the Bromate-Eruim-Malonic Rad System",98 J. AMER. CHEM. SOCIETY (No. 7) 1721 (1976); Arthur T. Winfree,"Rotating Chemical Reactions", 230 SCI. AMER. 82-95 (1974); Mrie L.Smoes, "Dissipative Structures in Chemical Oscillations withConcentrations-Dependent Frequency", 59 J. CHEM. PYS. 6277-6285 (1973);80 CATALYSIS, KINETICS (67) 52709j (1974); Richard J. Field, et al,"Oscillations in Chemical Systems II. Thorough Analysis of TemporalOscillation in the Bromate-Cerium-dMalonic and System", 94 J. AMER.CHEM. SOCIETY 8649 (No. 25) 1972; and John J. Tyson, "NonlinearOscillation In Chemical Systems", 58 J. CHEM. PHYS. 3919 (1973). Anobvious problem with this theory is that, at a given temperature, thecolor of the instant novel compositions are stable.

On the other hand, perhaps the color change of our phenomena if only aGroup III compound is employed is caused by a disturbance of thepotential field of the compound by the anion that either forms acovalent bond or comes into intimate contact with the compound moleculeduring separation of the dye from its solvent or crystallization.

Still another theory possibly explaining the Group III compound activityis as follows: many dyes are known to have a different crystalline colorthan when they are in solution, due to difference in absorbance of lightby the crystal surface from the absorbance of light by the solvated dyemolecule. Thus, this theory party explains why dyes, with color in theircrystalline state different than the color in their dissolved liquidstate, will show Group III activity with a change in phases.

Consideration for the application of this theory must include the natureof the phase diagram of the dye and solvent. If the solid solubility ofthe dye is significant, the color of the solid will be essentially thesame as the liquid. Also, if the dye and solvent form a low meltingeutectic, then at normal observation temperature there will remain someliquid phase composed of solvated dye. Thus, for a system to have aphase/color change, the phase relationship of dye in solvent must besuch that the amount of the dye-in-solid-solvent phase is very much lessthan the solid-dye and solid-solvent phases at temperatures below themelting point of the solvent.

From all the evidence presented by our studies, we think that thefollowing Group III mechanism for the thermometer is probably correct,i.e., that the change in color depends on the use of a dye, or mixture,whose color in liquid solution differs from that in the solid statebecause the solvent of varying melting point does not form completesolid solutions.

The case of the Group I-II combinations we think is simpler. It is ourbelief that there is little doubt that the large majority of these dodepend, as suggested above, on acid-base equilibrium which change onpassing from the solid phase to solution. In general, the solid phaseseems to contain more of the undissociated species, as might beexpected, since the ions formed by proton transfer shall be stabilizedin solution by solvation. Most of the cases cited also seem to takeplace by proton transfer. However, the possibility of Lewis-base-Lewisacid interactions may be considered by those in the art. Thus amines maycombine with cationic centers of cationic dyes to give solids of leucoamines, .sup..tbd.C⁺ +N.sup..tbd.→.sup..tbd.C-N⁺.sup..tbd.. A similarassociation may be possible in some cases between anionic and cationicdyes. Even if cases have not yet definitely come to light, this is apossibility which should certainly be considered. Another theoreticalpossibility is the use of two compounds, A and B, which together cangive rise to a change transfer band but which crystallize separately. Itis thought by Applicants that is would be difficult to obtain asufficiently intense color without using concentrations high enough tointerfere with the melting of the solvent over a small temperaturerange.

Concerning the relationship between structure and use in the GroupI-Group II combinations, the types of grouping that give rise topH-dependent color changes in view of the disclosure herein will be wellknown to those in the art since compounds of this type are used asindicators. Indeed, all the examples cited here are typical indicatordyes, combined with an acid. In order to obtain a color change onmelting, it is necessary to choose an acid-dye combination in whichproton transfer occurs on passage from solid to solution. Probablyalmost any pH indicator could be used in this connection in combinationwith a suitable acid.

As described above, the Group III compounds operate by showing a colorchange in their own right, between the crystal and solution in thethermometer solvent. The examples cited herein are generally, with smallexception, the "cyanin-type" dyes, conjugated with odd-conjugatedhydrocarbon anions. Dyes of this type, in particular the cationic ones,are known to those in the art to show color changes with concentrationand solvent changes and also when combined with biological materials("metachromatism", above). It now seems fairly clear that these changesare mostly due to association of the dye into polymers, the flat dyeions being stacked together like a pack of cards. The interactionsbetween the ground and excited states of individual dye ions leads to asplitting of the lowest transition. Of the resulting spectrum oftransitions, all except that of highest energy are forbidden, so theeffect is a hypsochromic shift. Similar effects are well known to thosein related arts in organic crystals (Davidson effect). For thepolymerization of the dye ions to be possible, the interactions betweenthem must be strong enough to overcome their mutual coulombicrepulsions. This can be so only if the ions are large (so that thecoulombic repulsion is minimal) and if they can approach closely so thatthe molecular orbitals (MOS) of different ions can overlap. For this tohappen, we believe that it is essential that the ions be planar and freefrom bulky obstructing groups. These conditions are met well by theorganic dyes themselves, which show dramatic color changes withconcentration in suitable solvents, and also by a variety of othercationic dyes. Other equivalent anionic dyes should be equally able toshow similar effects though fewer examples are known to us.

Confusion might be caused at first to those in the art by theobservation that the color changes might occur only in water as solvent.This at first glance might be thought to be attributed to binding of thedye ions in pairs by water bridges through hydrogen bonding. However,the examples cited by Applicants herein seem to indicate that the soliddyes also show colors different from those in nonaqueous solvents andthat the colors are similar to those of the polymeric species in strongaqueous solutions. This suggests to use that water cannot be involved inthe polymerizations. The X-ray crystal structures of a number ofcrystalline dyes of this type indicates however that they have thestacked polymeric structure postulated for the "abnormal" species insolution.

One skilled in the art might ask the logical question of how then doesthe water act? In a non-aqueous solvent of low dielectric constant, wethink that dyes of this type will exist as intimate ion pairs.Furthermore, since the gegenion is normally much smaller than the planardye ion, it will normally be held near to the middle of the flat face ofthe latter to maximize the coulombic attraction. For the dye topolymerize, it will then be necessary to remove the gegenion which islikely to require considerable energy. Removal of the gegenion can,however, be effected easily by using an ionising solvent in which thedye dissociates,. Since water is supreme among normal solvents in thisrespect, it is not surprising that dyes should tend to polymerize in it.

One in the art may further ask why then does the dye ever polymerize inthe crystal? We believe that in our nonpolar solvent, most of thesurface of the dye is taken up by solvent molecules. The associationbetween these and the dye ions being quite strong since the forcesinvolved are of charge-dipole type. For the dye to polymerize we havethen to remove both the gegenion and the solvent. In the crystal, thereis only the gegenion--and the loss of energy in moving this to one sidemay well be balanced by an increased overall Madelung energy.

Why don't all dyes of this type show similar color changes? There are anumber of factors we think that one skilled in the art will nowlogically consider:

(1) The dye molecules must be geometrically able to form polymericstacks;

(2) The Van-der Waals-type forces between dye molecules must besufficient to overcome their mutual coulombic repulsion. It would beexpected that the former would increase, and the latter decrease, withsize of the ion but there is no simple way in which the balance betweenthe two can be predicted in any given case.

(3) The perturbation due to polymerization must lead to a visible changein color.

(4) A special factor in the case of anionic dyes may be the tendency ofthe gegenion (usually Na⁺) to associate with oxygen atoms in the dye,since most of the negative charge in such dyes is localized on theterminal oxygen atoms. Polymerization may then take place by associationof dye ions by O⁻. . . Na⁺. . . O⁻ links and not by interactions. Saltsof large inert anions will present possibilities for Group IIIphenomena.

There are, however, several other factors that we think need to beconsidered and which may be exemplified by cases already studied.

First, there is the effect of size of crystal in the solid. At lowconcentrations, if the dye crystals are relatively large, much of thelight may pass through unaffected by the dye. The transmitted light willthen consist of a mixture of white light, and light which has beenstrongly affected by passage through dye crystals. In the case of a dyewith a very high extinction coefficient and appreciable absorption overthe entire visible spectrum, individual crystals may absorb completelyand so appear black. The solid phase in the thermometer will then appeargrey (white+black), regardless of the color of the dye in dilutesolution. There seem to be several examples of such behavior in thelist; e.g. pinacyanol iodide. This may also show an inheret inherentcolor change in the solid, which is masked by the effect postulatedabove.

Furthermore, even if the crystal does not absorb completely, the visualimpression of a mixture of white with the natural color of the dye maylead to an apparent change of hue. This we believe is responsible forthe color changes shown by some of the neutral dyes; e.g. Savinyl GreenB™ (No. 131 in Table II below).

This differential effect may also be responsible for the differences incolor observed in certain cases for mixtures of dyes with inert coloredcompounds; e.g. several of the mixtures with phthalocyanins. It isextremely unlikely to us that the phenomena is due to any kind ofchemical reaction between the true compounds or to any kind ofaggregation. It seems more likely to us that the phthalocyanin is morefinely divided in the solid state than is methyl red.

Finally, there seems to be one possible approach to the problem which wehave not yet explored, i.e. the use of merocyonin dyes. Cyanin-type dyesare characterized by having two or more possible classical structures,the color of the dye being attributed to resonance interactions betweenthem; e.g. ##STR1##

In typical dyes, at least two such structures have similar energies andso contribute equally to the dye. Since both are charged, this balanceis not affected by changes in solvent. A merocyanin dye is generallysimilar to a cyanin but neutral. As a result, there is just oneunchanged resonance structure, the rest being Zwitterionic; e.g.##STR2##

Here charges in solvent can greatly alter the balance between theresonance forms and hence the color, and similar large changes takeplace on passing from the crystal to solution. A dye of this type whichdoes not form solid solutions with the solvent, hence, should be veryeffective in the novel thermometers of our invention. In summary, webelieve that cyanin-type dyes will show differences in light absorptionbetween solid and solution in all cases where the crystal structure ofthe dye indicates that the dye ions are stacked together in closecontact. For this to happen, we believe that the dye molecules must beplanar and free from bulky groups that might hinder stacking.Furthermore, we believe most merocyanin dyes are likely to show colorchanges on passing from solid to solution.

Regardless of the theory one prefers, at this time an understanding ofthe phenomena is far from complete, and the phenomena discovered must bedescribed as only partially resolved.

An example of an especially preferred Group III compound is pinacyanoliodide at a concentration of 0.025-0.05 percent by weight. Whendissolved in an OCNB/OBNB solvent, the liquid composition is aneye-appealing brilliant blue. During solidification at room temperatureof the OBNB/OCNB solvent, the pinacyanol iodide becomes increasinglyconcentrated in the correspondingly decreasing proportion of liquid. Thepinacyanol iodide increases in concentration to the point that whensolidification of the composition is complete, the pinacyanol iodide,because of (1) its decreasing attraction to the solid OBNB/OCNB solvent,and (2) its apparent metachromatic-type behavior, is isolated in smallparticles around the crystalline structure of the OBNB/OCNB solvent andfrom the view of an observer turns the color of the entire compositionto an attractive rose. When the solidifying composition is seen by anyform of microscopy, the beads of pinacyanol iodide particles appearquickly on the surface of the crystalline solvent in an aggregate. WhenGroup I and Group II materials are employed (without the presence of aGroup III material), a similar phenomena is seen when viewed bymicroscopy at about two hundred to six hundred power.

The method preferably employed in designing a series of compositions ofmatter for use in a temperature-indicating device or thermometer is asfollows: first, two or more weakly polar or moderately polar aromaticsolvent constituents (that are inert toward the chosen Group I-IIIorganic moieties) which have melting points that most closely containthe predetermined temperature range desired to be tested are selected,e.g., one of the melting points of the two constituents must be equal orlower (preferably slightly lower) than the lowest temperature of therange, and the other constituent must be equal or higher (preferablyslightly higher) than the highest temperature of the range. Preferably,two analogous chemical structures (e.g., analogs, homologs and opticalisomers) having substantially the same molecular volume or having thesame crystalline structure (e.g., isomorphous) are selected if theyborder the temperature range to be tested. The temperature range isdivided up into increments, usually no smaller than 2/10° or 1/10° C.over the temperature range to be tested. Then, a liquidous curve of themelting point as a function of temperature is constructed for the solidsolution of the solvent constituents, herein for example,ortho-chloronitrobenzene and ortho-bromonitrobenzene as in FIG. 1, overthe temperature range to be tested. In FIG. 1 it will be noted that theband, exaggerated about 40 or 50 times, is defined by the dash lines εand ε' on either side of the liquidous curve in the diagram andrepresents in an exaggerated manner the limit of accuracy of temperaturemeasurements, i.e., approximately 1/10° C. or 2/10° F. It is desiredthat the percentage of organic moieties (Group I and Group II compounds,or one or more Group III compounds) be of a very small weight fractionof the total novel composition of matter in that when the organicmoiety(s) is added to the solvent system as the melting point of thecurve is affected by a shift toward a higher or lower temperature for agiven proportion of solvent constituents. Usually about 0.05 weightpercent moieties (Group I and Group II compounds or Group IIIcompound(s) shifts the temperature curve in a uniform manner less thanabout 0.5° C. (ε or ε' in FIG. 1) in one direction or the other over theentire length of the curve. By keeping the weight fraction of organicmoieties in the solvent system constant, one can determine ε or ε' in acurve such as FIG. 1 and adjust the curve to compensate for thedifference in melting point caused by the addition of the moieties. Thetemperature scale such as in FIG. 1 is then divided into the suitableincrement size, for example, 0.2° F. or 0.1° C. in human clinical use,so that the number of novel compositions of matter necessary for thetemperature range is determined. These are marked on the ordinate ortemperature scale from which the same number of abscissas or mol/weightfractions of one of the solvents may be determined for each of thetemperatures incrementally located in the range. For example, if oneselects a temperature range of 96.0° F. to 105° F. and one also desiresthe increment of temperature as 0.2° F., one would divide a chart suchas FIG. 1 into forty-five ordinates (96.0° F., 96.2° F., . . . 104.8°F.).

In preferable operation, the disposable thermometer for the clinicaltemperature as is shown in FIGS. 12-13 is so constructed with about0.025 weight percent pinacyanol iodide, and the remaining balance of thecomposition (except for nucelating agents, if any)ortho-chloronitrobenzene and ortho-bromonitrobenzene in the proportionsshown in FIG. 1, except that the temperatures are adjusted to be about0.3° C. high (increment "Δ") for the entire curve (even after ε or ε'has been determined) between 96° F. and 104.8° F., since the user of thedisposable thermometer is only instructed to insert the thermometer forat least about forty-five seconds to about one minute in the mouth (seespatula portion "F" of FIG. 12) under the tongue as far back as possible(and adjacent, to but on the inside of the lower teeth, with the tongueon top of the thermometer portion "F"). After the stipulated time, theuser removes the thermometer from the mouth and the temperaturecorresponding to the last blue dot is read by the user although thetemperature that would have been required to turn the pocket from liquidto solid over an infinite period is about 0.3° C. less than thetemperature of the mouth. Of course, the Δ can be adjusted lower, say,to about 0.2° C., if the user is instructed to spend a longer period oftime with the thermometer in place, or visa versa. An example of such athermometer is the TEMPA-DOT® READY-STRIP™ Single Use SterileThermometer, by the Info-Chem Division of Akzona Inc. (distributed byOrganon Inc., a subsidiary of AKzona Inc.).

Ignoring the effect of the organic moieties Group I-III of such atemperature curve for the purposes of this paragraph, one would thendetermine for any given temperature in the range of the novelcomposition of matter by first determining the proportion of solventconstituents such as ortho-bromonitrobenzene toortho-chloronitrobenzene. For example, using Table I listed below, for100° F. one would select a solvent system of 77.3 weight percentortho-bromonitrobenzene and 22.7 weight percentortho-chloronitrobenzene, if one chose to ignore the effects ε or ε' ofthe organic moieties Group I-III on the melting point curve such as thatlisted in FIG. 1.

Of course, it is preferred that the weight percent of organic moietiesbe kept to a slight amount such as under 0.05 percent, so that a curveδ=f (temperature) or δ'=f (temperature) could be constructed similar toFIG. 1 with a uniform temperature effect of the organic moieties on theliquidous curve.

                  TABLE 1                                                         ______________________________________                                        COMPOSITION IN WEIGHT PERCENT OF                                              PURE OCNB--OBNB                                                               APPROXIMATE                                                                   MELTING                                                                       TEMPERATURE  ORTHOBROMO-   ORTHOCHLORO-                                       °F.   NITROBENZENE  NITROBENZENE                                       ______________________________________                                        96.0         56.2          43.8                                               96.2         57.5          42.5                                               96.4         58.8          41.2                                               96.6         60.1          39.9                                               96.8         61.3          38.7                                               97.0         62.5          37.5                                               97.2         63.5          36.5                                               97.4         64.5          35.5                                               97.6         65.5          34.5                                               97.8         66.5          33.5                                               98.0         67.5          32.5                                               98.2         68.5          31.5                                               98.4         69.5          30.5                                               98.6         70.5          29.5                                               98.8         71.5          28.5                                               99.0         72.5          27.5                                               99.2         73.5          26.5                                               99.4         74.5          25.5                                               99.6         75.5          24.5                                               99.8         76.4          23.6                                               100.0        77.3          22.7                                               100.2        78.1          21.9                                               100.4        79.0          21.0                                               100.6        79.9          20.1                                               100.8        80.8          19.2                                               101.0        81.7          18.3                                               101.2        82.6          17.4                                               101.4        83.5          16.5                                               101.6        84.3          15.7                                               101.8        85.1          14.9                                               102.0        85.9          14.1                                               102.2        86.7          13.3                                               102.4        87.5          12.5                                               102.6        88.2          11.8                                               102.8        88.9          11.1                                               103.0        89.6          10.4                                               103.2        90.3          9.7                                                103.4        91.0          9.0                                                103.6        91.7          8.3                                                103.8        92.4          7.6                                                104.0        93.1          6.9                                                104.2        93.8          6.2                                                104.4        94.5          5.5                                                104.6        95.2          4.8                                                104.8        96.0          4.0                                                ______________________________________                                    

Once the organic moieties Group III compounds and/or Group I and GroupII compounds are determined for the desired color change, they are addedto a liquid mixture of the solvent constituents for the predeterminedtemperature and mixed, preferably by any suitable industrial mechanicalmixing means known to those in the art until a substantially completedissolution has been obtained.

After the solvent weight fractions have been determined and the novelcomposition of matter formed for each of the increment temperatures tobe tested, a suitable temperature-indicating device is constructed suchas the novel device described below having a plurality oftemperature-sensitive regions, preferably having cavities in aheat-conductive carrier such as aluminum wherein each novel compositionof matter corresponding to one of the pre-selected points along thetemperature curve fills one of the regions, preferably a cavity, in theheat conductive carrier device. A method and apparatus for depositingprecisly metered quantities of a temperature-sensitive composition ofmatter on a surface is taught by Pickett, et al., U.S. Pat. No.3,810,779 (1974), incorporated herein by reference, and the techniquesof that patent are incorporated herein as much as copied verbatim. Apreferable device for sealing a heat-sensitive transparent cover sheetmeans in vacuum-sealing engagement with an aluminum heat-conductivecarrier over cavities in the carrier is the Webb Model No. 2 machinemanufactured by Bio-Medical Sciences, Inc., in Fairfield, N.J.

Besides use in disposable oral thermometers, the novel compositions ofour invention may be employed for the detection of overheating inengines, for the detection of leaks from steam traps (the indicator maybe placed on an uninsulated piece of pipe just below the steam trap),for the detection of high temperatures in the surroundings of computers,home furnaces and appliances, as well as on packages for foods,forehead, skin and rectal temperature indicators.

As a preferred embodiment, we have found that film forming materialssuch as gelatin, polyvinyl alcohol, and water soluble cellulosederivatives are good barriers for containing small particles or dropletsof the novel compositions of matter of our invention, especially thecompositions wherein OCNB/OBNB is the solvent. After this form ofmicroencapsulation, a dry granular material is formed that is easilyadaptable to various machinery processes. A typical microencapsulatednovel composition would be an OCNB/OBNB solution containing 0.035 weightpercent pinacyanol iodide surrounded by a layer of gelatin coacervatedwith acacia and fixed with glutaraldehyde. The use of thesemicroencapsulated novel compositions would permit application totemperature-sensing devices with more flexibility. For example, themicroencapsulated novel compositions may be formulated into apressure-sensitive adhesive from which a temperature indicating tapecould be made. Microencapsulated novel compositions could beincorporated into printing presses to permit temperature sensing regionsof unlimited geometry including temperature-responsive messages.

2. Novel Temperature-Indicating Device

In FIG. 2, a novel temperature-indicator device is disclosed comprisinga flat, gradually curved, or substantially curvilinear heat-conductingcarrier means having one or more spaced cavities defined therein todetermine a like number of predetermined temperatures in a temperaturerange by means of a like number of different thermally-responsivecomposition of matter. Each of the predetermined temperature isassociated with a composition of matter that is substantially withoutimpurities, and may or may not be the novel compositions of matterstated above, but a composition of matter which does change from anopaque form when solid to a transparent liquid upon melting. The noveltemperature-indicating device comprises (1) a flat, gradually curved, orsubstantially curvilinear heat-conducting carrier with one or morecavities indented therein: (2) (in the absence of employing the novelcompositions of matter of this invention) an indicator means located atthe bottom of each of said cavities; (3) a transparent cover sheet meansin sealing engagement with the carrier means above and overlying each ofsaid cavities to form an enclosure between the walls of the cavity andthe transparency cover sheet means; and (4) a composition of matterwhich substantially fills the cavity and is adapted to change from asolid to a liquid at substantially the predetermined temperatureassociated with said cavity, except for a substantially spherical voidin the composition of matter between the bottom of the cavity and thetransparent cover sheet means.

Referring to FIG. 2, one will notice that colorant 1 fills the bottom ofa cavity "A" in a flat heat-conducting carrier means 2 of width 6 whichmeans is substantially filled with a "classical" solid solution 5. Thecavity "A" is covered by a transparent cover sheet means 4 which fits insealing engagement with heat-conducting carrier means 2 immediatelysurrounding cavity "A" and covering the solid solution 5 filling cavity"A". Within solid solution 5 is a substantially spherical cavity 3 whichhas a diameter 10 only slightly smaller than the width 12 of the cavityminus the small width 11 of the colorant 1. In the preferred embodimentshown in FIG. 2, the carrier means cavity is in the shape of a trapezoidrotated around its axis, having a large diameter 8 at the top of thecavity and a smaller diameter 9 at the bottom of the cavity. The width 7of the transparent film 4 is preferably substantially equal to the width6 of the heat-conducting carrier means 2. While the exact dimensions(6,7,8,9,11,12) of a cavity in items such as those in FIG. 2 vary withthe solvent system employed, the materials selected, and thecompositions of matter which is predetermined (whether or not one of thenovel compositions of matter described above or a classical compositionof matter which changes from opaque to transparent with change in phasesfrom solid to liquid), it is well to describe a device employingortho-chloronitrobenzene and ortho-bromonitrobenzene recentlyconstructed.

Referring again to FIG. 2, the heat conducting carrier means 2 is analuminum foil of width 6 of approximately 0.0003 inches (naturally, theheat-conducting carrier means 2 must be a material which has a highthermal conductivity and relatively large surface area of contact withthe test subject and be of minimum thickness, while preserving itsstructural integrity, in order to permit rapid conduction of heat intothe cavity such as shown in FIG. 2. Where aluminum is used, itsthickness may vary from about 0.001 inches to about 0.004 inches. In anyevent, the selection of such heat-conductive carrier means is wellwithin the knowledge of those skilled in the art and needs no furtherelaboration). In a particularly effective embodiment, theheat-conductive carrier means 2 is always preferably constituted ofaluminum or alloys thereof which transfer heat in an effective manner inthe alternative, the heat conducting carrier means may be made ofplastic. Thereby, the carrier is provided with the necessary strength toserve as the main structural support, while at the same time providingrapid and uniform temperature distribution throughout the thermometerdevice. As a consequence, the time required for taking temperature issubstantially diminished. The depth 12 of cavity "A" in FIG. 2 isselected to be preferably 0.004 inches, with the upper horizontal width9 being approximately 0.035 inches. The width 7 of the transparent filmis approximately 0.001 inches, the letter being a painted letter on thebottom of the cavity "A". As implied in FIG. 2, a layer 11 of colorantmaterial (paint) is stamped onto the bottom of each cavity "A" of avisible material that may be somewhat absorbed into the composition ofmatter or solid solution 5 upon melting of the "classical" solidsolution 5 to make the colorant material more visible (See FIG. 9). Thetransparent film cover means 4 may be polypropylene, Mylar,polyethyene-terephthalate nitrocellulose, polyvinyl chloride, etc. InFIG. 2, the transparent film cover means 4 is preferably aheat-sensitive material and is a coextruded film of Nylon 6®(manufactured by the Allied Chemical Company) and Surlyn 1652®(manufactured by E. I. duPont de Nemours & Company) which film isproduced by Pierson Industries Incorporated that is subsequentlylaminated to polypropylene by the Millprint Company of Milwaukee, Wis.

In each cavity "A", such as that shown in FIG. 2, one of thepredetermined compositions of matter that is associated with apredetermined melting point is poured into the cavity, fillingapproximately 60% of said cavity. After partial filling of each cavity"A" with a particular composition of matter (here OCNB:OBNB) associatedwith a temperature to be measured (here between 96.0° F. and 104.8° F.),transparent film 4 is put in sealing engagement with aluminum foil 2through the use of a machine such as the Webb Model NO. 2 manufacturedby Bio-Medical Sciences Inc. of Fairfield, New Jersey. Because of thesurface tension produced in the cavity "A", a substantially sphericalvoid 3 is formed in the cavity "A" which retains its character even uponmelting of the composition of matter. This cavity acts as a magnifyingdevice for the observer from above to see the colorant 1 which may ormay not be absorbed or partially absorbed into the composition of matterupon melting from the solid. As will be recognized by those skilled inthe art, small deviations could be made in ratios of the wdiths 6through 12, or alternatively, the ratios could be maintained fordifferent sized systems (e.g., by multiplying distances 6 through 12 bya uniform but different constant) without substantially affecting theresults of the invention.

FIGS. 3 and 4 are taken from sectional views [lines 3--3 and 4--4] ofFIG. 2 shown as the observer would see them from above the cavity "A" ofFIG. 2; FIG. 3 is a view of cavity "A" when empty of the composition ofmatter (8 in FIG. 3 or 1 in FIG. 2), while FIG. 4 shows a cavity filledwith the "classical" composition of matter after the "classical"composition of matter has melted and is transparent, so that theobserver has the apparent observation that the colorant 9 fills theentire bottom of the cavity "A", and in this case, partially absorbedthroughout the cavity "A". When the cavity "A" has been filled with thecomposition of matter 5, and the composition of matter is a solidsolution prior to its melting, the opaque characteristic of thecomposition of matter completely obscures sight of the colorant 1 at thebottom of the cavity "A". Hence, only when the composition of matter hasmelted can one see the colorant 1 at the bottom of the cavity "A" orthroughout the cavity "A". It is necessary that the melting substancesor composition of matter 5 in FIG. 5 be of such purity in nature thatupon melting completely, it has the property of "stable undercooling",or simply "undercooling" known to those skilled in the art, i.e., thatit has the property that after liquifying upon cooling at ambienttemperature below the freezing point of the composition of matter, itwill remain liquid for several hours. It has been found that if thecomposition of matter has the concentration of impurities indicatedabove, then it will have such a property of stable undercooling.

If the novel compositions of matter described above are used (instead of"classical" compositions that change only from opaque to transparentupon a corresponding change from solid to liquid) the layer of colorant1 may be eliminated.

FIGS. 5 and 6, respectively, present a partial plan view from above andthe side of one embodiment of the invention showing a heat-conductingcarrier means "C" of a thermometer in a Celsius system (one sub-gridshowing cavities associated with 35.5° C. to 37.9° C. only), and a planview from above a similar means of the same chemical thermometer in aFahrenheit system in a particularly effective embodiment of theinvention, to wit, a rectangular grid is formed (preferably having twosub-grids of 35.5° C. to 37.9° C. and 38.0° C. to 40.4° C. for theCelsius type and 96.9° F. to 99.8° F. and 100.0° F. to 104.8° F. for theFahrenheit system) wherein each caivty 13 employs a construction as inFIG. 2 and is clearly associated with a temperature to be determinedwithin the range of temperatures to be tested through markings locatedon the side of the grid. In FIGS. 5 and 6, one will notice that as eachcavity 13 employs the same colorant (1 of FIG. 2); so that upon acompletion of a test for the thermometer within the predeterminedtemperature range, one or more cavities having compositions of matter inthe liquid phase will clearly be distinguished from the remainingcavities having compositions of matter in the solid phase.

FIG. 7 indicates a scheme for testing temperatures of intervals of 10°F. using the novel compositions of matter described above (which turnsfrom orange 103 to red 104, for example, on melting) wherein thenecessity for colorant materials 1 of FIG. 2 is eliminated. Here in FIG.7, transparent cover plate means 101 is in sealing engagement,preferably vacuum sealing engagement, with the heat conducting carriermeans 102 and each of the peripheries of the six cavities shown. It willreadily be appreciated by those skilled in the art that the novelcompositions of matter can be used not only in the noveltemperature-indicating device shown in FIG. 2, but in otherconfigurations as well, such as FIG. 8, wherein a single cavity isemployed with the same novel composition of matter of FIG. 7 (that hasalready changed to red upon melting) to determine whether or not amaterial in storage has exceeded a safe temperature.

Referring again to FIG. 2, in the case of employing one or more"classical" composition(s) of matter, the colorant or dye layer 1 maycontain a dyestuff which is responsive to the change in the physicalstate of the composition of matter 5. The colorant 1 may be a "dyelayer", or layer constructed of a material impregnated with a dyestuff.Examples of dyestuffs suitable for indicator materials are thehalogenated nitrobenzenes such as Croceine Scarlett SS® and PolynalBlue®, both manufactured by the Allied Chemical Corporation, and bothstable over long periods of time. As the composition of matter 5undergoes initial melting, the dye layer 1 becomes wetted, resulting inthe substantially instantaneous migration of dye from layer 1 to theentire body of the composition of matter 5. However, it may be necessaryonly to employ colorant materials 1 which are merely paints at thebottom of cavity "A", preferably that are blue or black. The greater theintensity of the visible change of appearance in the composition ofmatter 5 through the employment of a substantially spherical void space3 and dark colorant layer 1, the greater the ease in reading thethermometer cavity. In one preferred embodiment, the change inappearance of the "classical" composition of matter 5 when seen fromabove, such as in FIG. 9, is from white to intense blue using a paintedindicator layer having the latter color.

The operation of the thermometer of FIG. 5 (or FIG. 6) is as follows:viewing FIG. 5 with cavities substantially constructed as in FIG. 2, theremote part of the handle portion "B" (not shown in FIG. 5, but 35 inFIG. 9) in FIG. 5 is held between the fingers, and portion "C" withcavities 13 is inserted into the mouth and preferably held under thetongue for a relatively short period, to wit, approximately thirtyseconds to one minute. During this time, all of the compositions ofmatter of the various cavities 13 which have melting points below thetemperature in the mouth will melt, revealing the colorant 1 in each ofsaid cavities to indicate a change in color visible to the naked eye.Because of the purity in nature of the melting compositions of matter,such that they have a property of stable undercooling for at leastseveral minutes, the user may simply withdraw the thermometer of FIGS. 5and 6 and clearly see via the grid shown thereon his temperature to theincrement of precision chosen, to wit, 0.2° F. or 0.1° C. Preferably,the colorant 1 for each of the cavities 13 in FIG. 5 is of the samecolor, and all of the cavities are filled by OCNB/OBNB compositions ofmatter having melting points separated by equal increments of 0.2° F. or0.1° C. whose constituents have been selected from a graph such asFIG. 1. FIGS. 9 and 10 display in another preferred embodiment in threedimensions from a skewed angle a flat heat-conducting carrier means 37,here aluminum, with cavities 36 (such as shown in FIG. 2) in aFahrenheit grid (as FIG. 6) from 96.0° F. to 104.8° F. connected to aplastic (preferably polystyrene, polypropylene, or polyethylene) handle35. Until used, the carrier means 37 fits comfortably inside a case(preferably made of the same materials as the handle 35) 32 and by meansof a roller 33 which exerts leverage downward against carrier means 37and a layer of paper, platic, or other retaining means 31 to prevent thecarrier means 37 from being removed accidentally from case 32 unless adeliberate force is exerted on handle 35 to accomplish such removal.Although not shown in FIG. 9, the end of the carrier means 37 (which ismost adjacent to handle 34) is fitted with locking means so as to make avacuum-sealing engagement between said carrier means 37 and case 32until a deliberate force of sufficient magnitude breaks the lockingmeans. Also, the handle 35 may be notched so as to form indentures 34therein for a firmer grip by the user who desires to remove the carriermeans 37 from the case 32.

In FIG. 10, once again a transparent cover sheet means 39 in the form ofa plastic transparent sheet or plastic transparent cover means fits insealing engagement, preferably vacuum sealing engagement, with thecarrier means 37 overlying and above cavities 36 and in sealingengagement with each of the peripheries of said cavities.

FIG. 11 shows a horizontal section along line 11--11 of FIG. 10; whichis a partial plan view of several cavities having indicator means 38 inthe form of a paint. Transparent cover sheet means 39 is in sealingengagement with aluminum heat conducting carrier means 37 and is insealing engagement with each of the peripheries of the cavities; asimilar bottom plate means 40 fits in sealine engagement with heatconducting carrier means 37 and is in sealing engagement with each ofthe peripheries of the cavities; a similar bottom plate means 40 fits insealing engagement with heat conducting carrier means 37 so as topresent the thermometer as a flat surface. The bottom plate meand 40 isprovided to aid the carrier means 37 in preserving structural integrityand is co-extensive with the entire surface of carrier means 37, and hasa thickness from about 0.001 inches to about 0.004 inches.

In FIGS. 12 and 13, another preferred embodiment of the invention isdisclosed for measuring temperatures at 0.2° F. increments from 96.0° F.to 104.8° F., combining the novel compositions of matter of thisinvention (preferably OCNB:OBNB/pinacyanol iodide) with the novelcavities of FIG. 2, only without the necessity of an indicator layer.Unlike the embodiment shown in FIGS. 9 and 10, the embodiment realizedin FIGS. 12 and 13 does not have a case, and therefore is less expensiveto manufacture.

FIG. 12 displays a plan view of the substantially flat oral temperatureindicting device as seen from above. Again, the thermometer has analuminum heat conducting carrier means 44 (of width 47 in FIG. 12) whichacts not only as a main structural body of support, but at the same timeprovides rapid and uniform temperature distribution throughout thespatula portion "F" (having width 54 containing grid "G" of a pluralityof cavities (each of diameter 57 and spaced center-to-center with eachneighbor along a horizontal "x" axis or vertical "y" axis in FIG. 12 ata distance 52 apart) of FIG. 2, each cavity with the novel compositionof matter and each associated with a predetermined temperature to bemeasured at 0.2° F. increments from 96.0° F. to 104.8° F., and eachnovel composition of matter substantially spherical void within saidcavity. "Spatula" portion "F" of the device of FIG. 12 is rounded forsafety so that some distance 56 is maintained between the most forwardrow of cavities and the edge of the device. It may be observed by thoseskilled in the art that if "classical" compositions of matter areemployed in lieu of our novel compositions of matter, that each cavitywill necessary employ an indicator layer such as layer 1 of FIG. 2.

Again in FIG. 12, one will note that the aluminum heat-conductingcarrier means is covered above for the entire handle "E" portion of thethermometer device by a top plastic layer 42 of width 54, preferablymade out of a plastic such as polystyrene, polypropylene, orpolyethylene. In FIG. 13 a bottom plate means 46 of width 49 extendsalong the entire length 53 of the thermometer device. The top layer 42terminates upon entering the spatula portion "F" of the thermometerdevice, revealing grid "G" of cavities, dark markings (preferably blueor black-painted) 45 indicating the predetermined temperature to bemeasured for each cavity, and a heat-sensitive transparent film covermeans 43 of width 50, which as before is most preferably a coextrudedfilm of Nylon 6® and Surlyn 1652® produced by Pierson IndustriesIncorporated that is subsequently laminated to polyproplyene by theMillprint Company, or in the alternative, simply Mylar, polypropylene,nitrocellulose, polyvinyl chloride, etc. The heat-sensitive transparentfilm cover means 43, as in FIG. 12, is in sealing engagement with thecarrier means 44 above, and is overlying each of said cavities to forman enclosure between the walls of each cavity and the transparent coversheet means 43. It is important the film cover means 43 be in tightvacuum-sealing engagement with the periphery of the carrier means 44with each cavity to avoid loss of the compositions of matter within eachcavity. For that reason, as well as for appearances, some minimaldistance 55 is maintained between a leading edge of a row of cavitiesand the edge of the thermometer device. Preferably, the heat-sensitivetransparent film cover means 43 consists of bands that cover only theimmediate area surrounding the cavities to avoid undue manufacturingexpense. (In FIG. 13, the transparent film cover means is shown in twobands, each of width 51 which covers the two rows of cavities), althoughit will be obvious to one skilled in the art that the heat-sensitivetransparent film cover means could cover the entire spatula portion "F"of the device. The heat-sensitive transparent film cover means 43 may beput in sealing engagement with aluminum carrier means 44 through the useof a machine such as Webb Model No. 2 manufactured by Bio-MedicalSciences, Inc., of Fairfield, N.J.

Also in FIG. 12, it will be recognized that the handle "E" has beenstamped from below so as to make the device realize two ridges, ribs, orabutments 41a that protrude from above the carrier means 44 by somenominal distance which is approximately the same as width 47 of carriermeans 44; likewise, the device realizes two cavities 41b in carriermeans 44 that parallel the ridges 41a. As will be appreciated by thoseskilled in the art, although the distances shown in FIGS. 12 and 13 canbe readily adjusted with respect to one another or in proportion (widths47, 48, 49, 50, 51, 52, 53, 54, 55, 56, 57, and 58 can be multiplied bydifferent constants) it is well to describe a device for measuring humantemperatures in the range of 96.0° F. to 104.8° F. that we recentlyconstructed, employing ortho-chloronitrobenzene andortho-bromonitrobenzene in a solvent system with pinacyanol iodide inthe amount of 0.035% by weight to form a thermometer with the novelcompositions of matter of this invention, which is the best mode of ourinvention and which is marketed by Organon Inc., (West Orange, N.J.)under the trademark Tempa DOT READY STRIP®. Referring again to FIG. 12,the thermometer has a width 54 of about 0.345 inches at the widestportion of handle "E" and has the same width 54 of about 0.345 inches inthe spatula portion "F" of the thermometer. The cavities each have adiameter 57 of about 0.039 inches and each cavity has a depth of about0.005 inches, and is spaced from each neighbor on a horizontal "x" axisor vertical "y" axis by a distance 52 of 0.015 inches. The top andbottom rows of cavities are of a distance 55 of about 0.039 inches fromthe leading edges, respectively, of the thermometer, and have a centerline on the right-hand column which is a distance 56 of about 0.193inches from the tip of the rounded edge of the spatula "G" portion ofthe thermometer. In FIG. 13, taken along line 13--13 of FIG. 12, it willbe appreciated that the oral thermometer device has an overall length of4.250 inches, and consists of an aluminum heat conducting carrier means44 having an overall length of 4.250 inches and a depth 47 of about0.003 inches. The aluminum heat conducting carrier means 44 is coveredon the handle portion "E" of the thermometer by a polypropylene orpolystyrene layer of thickness 48 of about 0.003 inches; the carriermeans also is in engagement with a polypropylene or polystyrene bottomplate means 46 of width 49 of about 0.003 inches that traverses theentire length of the thermometer. Two bands of heat-sensitive material(coextruded film of Nylon 6™ and Surlyn 1652™ subsequently laminated topolypropylene)) cover the two sub-grids (100° F. to 104.8° F. and 96.0°F. to 99.8° F.) and are each of width 51 of approximately 0.300 inchesalong the "x" axis and of depth 50 of from about 0.003 to about 0.005 linches.

As previously stated, grid "G" in FIG. 12 consists of two sub-grids, onefrom 96.0° F. to 99.8° F. and the second from 100° F. to 104.8° F. Inthis pattern, the cavities are arranged in rows along the longitudinalaxis of the thermometer. Although the two sub-grids selected were merelyfor convenience, one large grid could have been selected for the device.The group associated with the lower temperature value is positioned moredistantly from the thermometer handle while the group associated withthe higher temperature value is positioned nearer to the thermometerhandle. The temperature scale utilized Fahrenheit or Celsius) and thedesired range of measurements and temperature increments will quiteobviously determine the exact number of cavities and therefore rows.

Although not shown, a thermometer similar to that shown in FIGS. 12 and13 could be constructed whereby the bottom plate means (46 in FIG. 13)could be removed from spatula portion "F" of the device, and each of thecavities allowed to protrude entirely through the carrier means (44 inFIGS. 12 and 13); a bottom heat-sensitive and transparent film covermeans could be placed in sealing engagement with the carrier means theperipheries of each of the cavities so that one could observe the changein color of the novel compositions of matter if the latter wereemployed. Also, it is obvious to one skilled in the art that ribs 41a inFIG. 12 are not necessary; indeed, many minor changes in the deviceshown in FIGS. 12 and 13 could be made without departing from the spiritof the invention. As a preferred embodiment, ribs 41a may be removed asin actual pracrtice (TEMPA-DOT® READY-STRIP™ disposable clinicalthermometer of Organon Inc., West Orange, N.J.). The spherical void ofFIG. 2 is not required for the embodiment of FIGS. 12-13 when novelcompositions are employed.

FIG. 14 is a plan view of a elongated monolithic support member(preferably transparent) for a disposable clinical thermometer such asdepicted in FIG. 10 or in FIGS. 12-13. The support member is preferablymade of highly translucent polypropylene, although it will readily benoticed by one skilled in the art that the support member could, in thealternative, be constructed of any suitable maleable, soft material formso as to support the thermometer, yet flexible enough to avoid damagingdelicate tissue of the user. The support member is intended specificallyfor rectal administration of the thermometer, such as for infants andthe elderly or others who might otherwise not be capable of receivingoral administration properly. The member can also be used foradministration in any body cavity indicative of the temperature of thebody and of sufficient dimensions to accept the member.

Referring to FIG. 14 as before and now also FIGS. 15-16, it will beapparent that FIGS. 14-16 are taken from the vertical, and moreparticularly, that FIG. 15 depicts in plan view the translucent supportmember, except in sealing engagement with a disposable thermometer asshown in FIG. 10 with a Fahrenheit scale from 96.0 to 104.9 degreesFahrenheit with 0.2 degrees Fahrenheit increments. FIG. 16 is identicalto FIG. 15, except utilizing a Centigrade scale from 35.5 degreesCentigrade to 40.4 degrees Centigrade with increments of 0.1 degreesCentigrade. Body 61 of the member acts as a bridge between the sections"H" and "I", which are adapted to fit comfortably spatula portion "F"and handle portion 42 of the disposable thermometer in FIG. 12,respectively, in sealing engagement. Section "I" comprises a handleportion 64 with a ridge or indentation 63 as seen from above and facingthe user in FIG. 14 and above but away from the user in FIGS. 15-16,i.e. as if the member of FIG. 14 was merely rotated on its axis 180° toreceive the Fahrenheit thermometer of FIG. 15 or the Centigradethermometer of FIG. 16. Ridge 63 continues into body 61 as ridge orindentation 62 which traverses the entire support member on both sidesof the member into section "H". The ridge is of sufficient width (about1 cm) to accept the thermometer comfortably and to alleviate the problemof cutting during insertion into the body cavity, and is of such atolerance that the disposable thermometer of FIGS. 10 or 12 snapssecurely into fitting engagement with the member. The spatula tip 65 ofsection "H" is rounded smoothly, as are exterior edges of the member, inorder to avoid damage to delicate tissue upon administration of thethermometer. Spatula portion "H" is suitably constructed to have awindow or vacancy so that the grid of the thermometer such as grid "G"of FIG. 10 is clearly seen upon removal from the source by the user.

As a most preferred embodiment, and referring again to FIGS. 14, 15 and16 display a rectal adapter including forward section "H" and rearwardsection "I". Forward section "H" includes substantially solid top 65which is the leading edge of the rectal adapter during insertion intothe rectum. Tip 65 is a partially flattened conical shape for comfortduring insertion. The inside bottom portion 64 of the rectal adapterreceives the bottom portion 42 of thermometer of FIG. 12. Thethermometer is adapted to be snap-fitted into the adapter by means oflips 62 and 63 which extend about a portion of the periphery of theadapter. As can be seen, lip 62 extends outwardly from the bottomsurface of the adapter and inwardly towards its longitudinal axis. Therearward portion 12 of the adapter further includes a handle receivingportion 63 for the receiving handle 42 of the thermometer. Otherembodiments of disposable thermometers do not utilize a handle and thushandle receiving portion 16 would act as a handle itself or could beeliminated.

Again referring to FIGS. 15 and 16, the forward section "H" of theadapter further includes an open window portion which is adapted toalign with thermally-responsive temperature indicating portion of thethermometer of FIGS. 12 and 13. This window is in effect a hole punchedthrough the adapter for provding improved thermal contact fortemperature indicating portion of the thermometer and its immediateenvironment.

FIG. 14 also shows the thermometer of FIG. 12 snap-fitted into a rectaladapter with the top side of the indicating portion facing the user andpartially covered by an open window shown in Section "H". FIG. 15 alsoshows the rectal adapter with the temperature indicating portion of thethermometer 1 exposing pockets directly to its surrounding environmentthrough the open window in Section "H". The use of the thermometers ofthe prior art with prior art rectal adapters did not permit the bottomside of the thermometer thermally-responsive material to be exposed tothe environment. That is, the pockets such as 43 of FIGS. 12 and 13rested against the polypropylene material on the inside bottom layer ofthe pripr art rectal adapter. Since the rectal adapter of the prior artwas normally made of a plastic, such as polypropylene, and since theseplastic materials are thermal insulator, it was found that thethermometer, when used with the prior art rectal adapter, registeredlower than a mercury and glass thermometer. Furthermore, clinicalstudies have shown that the use of the disposable thermometers with theprior art rectal adapter did not "fire", that is, some of the dotsbetween the highest temperature dot fired and some lower temperaturedots did not even register, thus providing a confused reading to theobserver. Furthermore, if the indicating portion of the thermometer wasinserted face down into the prior art adapter, the thermometer could beread only by removing it from the adapter. The instant adapter exposesboth sides of the thermally-responsive portion of the disposablethermometer to its immediate enviroment by providing an open window inthe rectal adapter thermally-responsive portion of the thermometergreatly improving the accuracy and response time of the thermometer. Ithas been shown by experiment that rectal temperatures taken using theimproved rectal adapter/disposable thermometer combination provides thesame temperature readings as a 3-minute glass and mercury thermometerreading. The disposable thermometer, however, provided the readingwithin 11/2 to 2 minutes. Furthermore, experiments showed no tendencyfor the disposable thermometer to register "no fires", or skips, as didthe thermometer used with a prior art rectal adapter. Because of thewindow, the thermometer may be easily read without removing it from therectal adapter even if the thermometer has its indicating portion facedown in the adapter. Thus, the window in the improved rectal adapterprovides a dual function of improved thermal transfer characteristicsand ease of reading for the thermometer.

As stated previously, one of the problems with the prior art adapter isincorrect low thermometer readings due to the fact that the adapter maybe made of plastic insulators with the thermal conductivities listedbelow:

    ______________________________________                                        polypropylene  2.8 × 10.sup.-4 cal-cm/sec/cm.sup.2 /° C.         polyethylene   8-12 × 10.sup.-4 cal-cm/sec/cm.sup.2 /° C.        polyvinylchloride                                                                            3-4 × 10.sup.-4 cal-cm/sec/cm.sup.2 /° C.         polycarbonate  4.6 × 10.sup.-4 cal-cm/sec/cm.sup.2 /° C.         polystyrene    1-3 × 10.sup.-4 cal-cm/sec/cm.sup.2 /°            ______________________________________                                                       C.                                                         

Thus an operable adapter utilizing applicants' invention may be madefrom the same or similar materials enabling correct thermometerreadings.

From the foregoing description of the adapter, it would be apparent thatmany modifications may be made therein. For example, the thermometer ofFIG. 12 may be placed into the adapter with either the pockets 22 facingup or down. It is therefore intended that such modiciations shall becovered by the appended claims.

In still another embodiment to this invention, we have found that onemay add an additional and effective amount of a soluble suitablenucleating agent, here a small amount of anthraquinone, to the existingnovel compositions of this invention (or just to "classical"compositions of matter which will change from opaque to transparent upona change from solid to the liquid state, or vice versa) which limits theamount of undercooling that the novel composition of matter (or even"classical" compositions of matter) can experience. Previously, (Chadha,U.S. Pat. No. 3,956,153) those skilled in the art employed anthraquinonein a "saturated"amount (e.g., from about 0.7% by weight to 0.9% byweight) in disposable thermometers in order to assure that thedisposable thermometer (such as one employing OCNB:OBNB systems, such asshown in Table I) did not become molten prior to time of usage becauseof accidental or inadvertent melting due to high storage or shippingtemperatures (see U.S. Pat. No. 3,980,581). However, we have discoveredunexpectedly that anthraquinone may be employed in an effective amount,which is a somewhat lower content, e.g., from about 0.01% to about 0.4%by weight, in order to allow the user to induce resolidification of thethermometer at a predetermined controlled temperature below the meltingpoint of the novel (or "classical") composition of matter. In thismanner, the thermometer can utilized the undercooling principle toindicate accurately for a substatial period of time a temperature uponwithdrawal of a heat-conducting carrier means containing a grid ofcavities from the mouth, and also be regenerated or made reusable byplacing the thermometer (e.g., the heat-conducting carrier with the gridof cavities) in cold water (e.g., 32° F. -40° F.) or another convenientlow temperature medium which would lower its temperature to a pointwhere nucleation sites would be formed in the supercooled liquid causinga spontaneous solidification of the novel (or "classical") compositionsof matter, with its indicator additives. At that time, the thermometerwould change from its liquid phase color (for example, red in the caseof a OCNB/OBNB system with chlorophenol blue and ethyl red) back to itssolid phase color (yellow). This embodiment would make the noveltemperature-indicating device of our invention, whether employing thenovel compositions of matter or the "classical" compositions of matterwith the indicator means being a painted layer, etc., capable ofmultiple uses, thus representing a substantial advancemenet in thetechnology of chemical thermometry.For examples of other suitablenucleating agents, see U.S. Pat. No. 3,980,581, column 5 and 6incorporated herrin by reference and especially column 6, lines 26-49listing equivalent alternatives to anthraquinone.

As a much preferred embodiment, from about 0.01 weight percent to about1.0 weight percent of an insoluble nucleating agent, talc (TalcumPowder, USP, Mg₂ (Si₄ O₁₀ (OH)₂), which may be obtained from Whittaker,Clark & Daniels, Co., South Plainfield, NJ. (#399 Magnesium Silicate),may be employed in the novel compositions of matter as a means tocontrol the temperature of resolidification in a pinacyanoliodide/OCNB-OBNB system adopted for clinical use with the 0.1 weightpercent talc addition, regeneration or recrystallization occurs at about-6° C. Inter alia, potassium ethyl sulfate or potassium pyrosulfate ineffective amounts are suitable alternatives to talc; see U.S. Pat.No.3,980,581, of which Col. 6, lines 7-49 are incorporated herein). Itmust be noted that some routine experimentation is necessary todetermine whether or not a nucleating agent is inert, i.e., whether ornot it will affect the change in color upon change in phases of thenovel compositions of matter. For example, some nulceating agents suchas hydroxylamine hydrochloride act as a strong acid and will decolorizethe dye portion of the composition; for example, a pinacyanoliodide/OCNB-OBNB composition. Others, Floricil, for example, will form apigment "lake" ("laking") within the dye and render the novelcompositions inoperable. Other potential nucleating agents, such aspotassium acetate or sodium tetraborate contain substantial quantitiesof water which when released upon crystallization will deactivate someof our novel compounds by dissolving and partitioning the dye (forexample bromochlorophenol blue) in the aqueous phase. Also, the watermay affect the melting point of the solvent.

We have found that about a preferable amount of 0.1 weight percent ofthe recited talc in a composition of 0.035 weight percent pinacyanoliodide and the balance OCNB/OBNB (contained within a package ofSURLYN®1652 by E. I. duPont deNemours & Company, and aluminum) willraise the temperature of recrystallization from -40° C. to about -6° C.

As an alternate to the nucleating agents mentioned above, the surface ofthe heat-conducting carrier may be treated by anodizing (anodicoxidation) or chemical passivation to create nucleating sites. Theanodizing procedure may be carried out in e.g. sulphuric acid orphosphoric acid or under other circumstances as will be known to thoseskilled in the art. Chemical passivation of the surface may be carriedout by an etching procedure in 2% sodium hydroxide, a subsequenttreatment with 10% nitric acid and washing with water.

In yet another preferred embodiment of the invention, and as analternative of employing a substantially spherical void of FIG. 2, onemay employ a circular layer of suitable absorbent bibulous material,which may be loaded with the novel composition(s) of matter, and thatsubstantially fills not only the space of the solution 5, but also thevoid space 3, and is impregnated with the novel compositions of matterof the instant invention. Viewed from above, as in FIG. 5, each of thepockets 13 appear to be a fully colored dot which is surprisingly aseasy, if not easier, for the user to read as the pockets of FIG. 2employing a substantially spherical void space. Of course, the bibulousmaterial must be inert to the phenomena of the novel compositions ofmatter upon changing phase. One material which has been found to beespecially suitable is E. I. duPont deNemours & Company, spun-bondedpolyolefin TYVEK®. Other suitable materials may include aggregatedinorganic powders, glass fiber paper, ordinary cellulosic paper, orother permeable polymeric material. An additional advantage of employinga bibulous material is that in case of accidential rupture oftransparent film cover means 43 (FIG. 13) by the user, for example, bythe teeth, the bibulous material would prevent spillage of the liquidcontents on the surroundings. Another advantage of the employment ofbibulous material is that instead of relying on the expertise of askilled operator to meter the amount of liquid novel compositions toeach cavity through the careful adjustment of many variables of afilling machine such as that depicted in U.S. Pat. No. 3,810,779 (suchas hydrostatic head, flow rates, cycle time, and interfacial tension)can be eliminated since the capacity of the bibulum is predetermined forthe size of the cavity and material employed. Thus, the open end of thefilling system will contact the bibulum (when previously installed inplace in the cavity) and liquid will contact the bibulum and liquid willquickly saturate the bibulum; driven by the capilliary attraction of theliquid to the bibulum, the flow will stop when saturation is reached. Astill further advantage of the invention is that it provides forflexibility in the geometry of the display-symbols, such as letters andnumbers, of other than dot or grid geometry, which be juxtaposed (asshown in FIGS. 5 and 12) or messages constructed from the novelcomposition(s) loaded on the bibulum.

Another preferred temperature indicating device consists of a layer ofan absorbant material (bibulum) in which the novel composition of matterhas been absorbed and which is surrounded by two transparent coversheets in a sealing engagement with each other.

Another type of operation can be developed for application to suitabledevices. The novel composition can be loaded onto a web of bibulum,solidified and then processed (e.g. by die cutting for example) intovarious devices simplifying manufacturing and reducing capital costseven further as the necessity for hot liquid loading of the novelcompositions into the cavities is eliminated.

It is noted that if the duPont SURLYN®1652 sealing layer aforementionedis replaced by a suitable structure comprising polyisobutylene (PIB byBASF, B-15™), then the novel liquid compositions inside each cavitysometimes remains pooled in a "dot" configuration instead of a "donut"or ring display of FIG. 2. It is believed that this phenomena isdifferent from that phenomena observed when SURLYN®1652 is employed,because the interfacial tension of the novel liquid composition (herepinacyanol iodide of about 0.025-0.05 weight percent/OBNB-OBNB asbefore) to the SURLYN®1652 is very low while the interfacial tension ofthe novel composition to PIB is extremely high. Thermodynamics predictsthat when materials are lqiuid and are physically free to move about,that they will occupy the lowest energy configuration. Hence, ifSURLYN®1652 or other SURLYN® adhesives are employed in the clinicalthermometer of FIGS. 12-13 with the novel compositions, the lowestenergy configuration is with the novel composition drawn against theSURLYN®, and particularly in the region where the SURLYN® forms a narrowcapillary with the circumference of the aluminum base (44 of FIG. 13).With PIB adhesives (by BASF, B-15™) it is believed that the novelcomposition is "repelled" by the surface of the adhesive (compared tothe aluminum base 44 and instead remains spread against the aluminumwith which it has a lower interfacial tension.

Furthermore, we have found, unexpectedly, that a bibulous materialraises the resolidification temperature of the compositions of matter(when in a supercooled state) to a level higher than heretoforeexperienced by solid inorganic nucleating agents. Therefore, byemploying TYVEK® or other suitable bibulous material, an easilyregeneratable thermometer (placing the fired thermometer into arefrigerator at about 40° F.) of a design substantially similar to thatshown in FIGS. 12-13 can be produced. Otherwise, without the use of thebibulous material, temperatures of -40° F. to -50° F. are needed toregenerate a fired thermometer. In this manner, thermometers which have"fired" because of excessive heat in transit or storage may be salvagedeasily. Bibulous materials have been used for the determination ofglucose and other substances in liquids; U.S. Pat. No. 4,059,407.

A further advantage of a bibulous embodiment is that the bibulum may beused as a carrier for the inclusion of other hard-to-handle materialssuch as finely powdered insoluble nucleating agents. Thus, if talc isemployed as a nucleating agent, it may be first loaded onto the bibulum.Such loading can be accomplished by passing the web through a dispersionof powder and then by evaporating the solvent. Bibulum material can bepunched in predetermined configuration; the punched bibulum can carrypredetermined quantity of the nucleating agent to each and every cavityof the thermometer pocket(s) or other device employing the novelcompositions of matter.

Many items of commerce are subject to degradation or destruction byexcessively high temperatures, and as recited before, single-useclinical thermometers employing the novel compositions of matter of theinstant invention are no exception, especially when a nucleating agentis not employed. Exposure of the clinical thermometers above 96° F. willcause them to "fire", i.e. to record the exposed temperature and becomeunusable for further temperature measurement unless an effective methodof recrystallization is employed. If no nucleating agent is employed ina composition having OCNB/OBNB as a solvent, means to lower thetemperature of the thermometer from -40° C. to -50° C. will benecessary, which means is sometimes unavailable to the user. Typically,products such as clinical thermometers are shielded from adverse effectsof high shipping and storage temperatures through heavy insulatedshipping cartons containing ice (solid water) as refrigerant--a methodwhich has obvious shortcomings.

We have discovered, unexpectedly, that protective packaging of heatlabile goods can be greatly improved by using certain salts, notablysodium sulfate decahydrate, e.g. Glauber's salt, as the refrigerant.Glauber's salt acts as a refrigerant as follows: the melting point ofGlauber's salt is 32.28° C. The TEMPA-DOT® READY-STRIP™ begins toindicate temperature at 35.2° C. When TEMPA-DOT® READY-STRIPthermometers are packaged with Glauber's salt and exposed to hightemperatures, for example 50° C., the temperature of the package risesuntil it reaches 32.28° C. At that temperature the Glauber's salt beginsto melt and absorb heat (energy) at a capacity of about 54 cal/gram. Thepackage will remain at about 32° C. until the salt has been consumed.

Ice, on the other hand, can only be loaded into the package immediatelybefore anticipated thermal abuse since it will melt and lose itsrefrigeration capacities in storage at normal temperature (i.e.approximately 70° F.).

A further advantage of the invention over commonly used refrigerationrelates to its ability to preserve the goods for extended periods oftime. The rate of thermal conductivity through any material, includinginsulation, is directly proportional to the difference in temperature oneither side of the material or insulation. When ice is used asrefrigerant in an exposure to 100° F. the difference in temperature is68° F. since ice performs most of its refrigeration during melting at32° F. With Glauber's salt, however, the difference in temperature isonly 10.4° F. (100° F.-89.6° F.). Thus, the rate of heat flow withGlauber's salt is less than 1/6 the rate of heat flow with ice asrefrigerant. The result of the differences in temperature and heat offusion between Glauber's salt and ice is that one pound of Glauber'ssalt will preserve the goods in the package as well as 4.5 pounds of iceduring exposure to 100° F.

For the application of preserving single-use thermometers sodium sulfatedecahydrate or calcium chloride hexahydrate are well suited, otherthermally labile goods or applications may require alternate salts orcompounds. The refrigerant should be selected as one having a meltingpoint 3°-5° C. below the labile temperature. The amount of refrigerantis dependent upon the thickness of insulation and surface area/volumeratio of the package, the amount of time and the temperature for whichthe goods need protection. An example of another usable salt is sodiummetaphospate trihydrate (e.g. Knorre's salt) which melts at 53° C. andcan be used to protect things labile at 57° C. There are many moreexamples of usable inorganic compounds (e.g. Potassium iron (III)sulfate 0.24 H₂ O, MP=28° C.) but organic compounds may be substituted.Thus, Glauber's salt may be replaced with o-chloronitrobenzene in theapplication with single-use thermometers.

It is desirable to package the novel refrigerant as with the classicalrefrigerant, ice. The novel refrigerant may be sealed in a flexiblepolypropylene plastic bag or closed in a rigid container. The purpose ofsuch a package is to prevent contamination and moisture exchange to takeplace as well as to prevent the molten refrigerant from contaminatingthe goods being thermally shielded.

While the use of the above "novel refrigerants" has many advantages,there are some minor problems. First, unless cast into a solid block,the novel refrigerants are generally formless powders which can bedifficult to handle. Further, upon melting, they form liquids which arefree to flow into new geometrics within their container, if flexible.

We have found that these novel problems can be overcome by absorbing themolten novel refrigerant into a bibulous material such as open cellfoam, paper, natural or synthetic sponge and the like, sealed to excludecontamination and, for hydrated salts, water vapor exchange by enclosingthe structure in a flexible plastic bag, for example.

The novel refrigerant so packaged, is easy to handle, retains its shapewhen the refrigerant is molten and prevents the refrigerant from saggingfrom its intended location within the package.

An example of such a packaged novel refrigerant is sodium sulfatedecahydrate absorbed into a block of open cell phenol-formaldehyde foamand contained in a polyethylene bag closed by heat sealing. When placedin an insulated container, the novel refrigerant block protects thecontents from exposure to high temperature in the same fashion as theunsupported Glauber's salt.

As a preferable example of containing disposable thermometers asdepicted in FIGS. 12-13 with the novel compositions of matter (such aspinacyanol iodide/OCNB-OBNB) one may ship and store about two thousandthermometers in a standard cardboard box of outer dimensions 93/4 incheswide by 135/8 inches long by 151/2 inches high (top and bottom 93/4inches by 135/8 inches; two sides 93/4 inches by 151/2 inches; two sides135/8 inches by 151/2 inches), by placing in the box square pieces(preferably six) of close cell polyurethane foam of 11/2 inchesthickness adjacent to the sides, top, and bottom of the box and placingthe aforementioned polypropylene-wrapped squares of sodium sulfatedecahydrate (thickness of about 1/2 inch to 1 inch) inside thepolyurethane foam. Pieces of such a container are easy to manufactureand assemble.

It must be noted that a preferred method of individually wrapping thethermometer of FIGS. 12-13 is by wrapping them in an envelope (here 11/8inches wide by 4 11/16 inches long) of bleached paper sealed on theedges by a suitable contact adhesive known to those in the art. Suchenvelopes are readily available at a reasonable cost from ModernPackaging Inc., Mount Holly, NJ. More elaborate methods of individuallywrapping the thermometers are available, e.g. U.S. Pat. No. 3,835,990,incorporated herein, but are not necessary if the above precautions aretaken for shipping and storing (using the Glauber's salt, etc., whenambient temperature is above 96° F. and otherwise preventing exposure totemperatures above 96° F.).

In one preferred embodiment the transparent cover sheet and the heatconducting carrier means of the above FIGS. 1-16 are preferably bondedtogether by means of a layer of a pressure sensitive adhesive whichentirely or substantially consists of polyisobutylene, as shown in FIGS.17-18.

More specifically, a temperature-indicating device heat-conductingcarrier may be employed having one or more spaced regions definedtherein to determine a like number of predetermined temperatures in apredetermined temperature range, with a like number of differentcompositions of matter defined therein, contained by a transparent coversheet means in sealing engagement with the carrier, and with a singlecomposition of matter being deposited in each of said regions and beingassociated with a single one of said predetermined temperatures whereinthe compositions of matter used are the novel compositions of matter ofthis invention and wherein the transparent cover sheet means and theheat-conducting carrier are sealed to each other by means of an adhesivelayer of a pressure-sensitive adhesive which entirely or substantiallyconsists of polyisobutylene.

In addition, in a similar way polyisobutylene may be used as an adhesivein any temperature-indicating device comprising:

(a) a heat-conducting carrier means provided with one or more cavitiesat least one of which cavities is filled with an indicator means and aclassical composition of matter which melts at a predeterminedtemperature and is composed of a mixture of ortho-chloronitrobenzene andortho-bromonitrobenzene, and

(b) a transparent cover sheet in sealing engagement with the carriermeans overlying each of said cavities.

From the U.S. Pat. No. 3,002,385, temperature-indicating devices areknown in which use is made of low-temperature bonding adhesive, such asan epoxy resin or a pressure-sensitive adhesive substance having a basisof silicones. For various reasons, such as insufficient resistance tothe chemicals used, release of low-molecular constituents, whichdetrimentally affect durability, temperature indication andreproducibility, and the fact that they are insufficiently impervious tochemicals, said adhesives have been found to be unsuitable.

It is preferred that the polyisobutylene used as pressure-sensitiveadhesive should have an average molecular weight in the range of 50,000to 5,000,000, more particularly 150,000 to 4,000,000.

A very favorable combination of adhesive strength and resistance to thechemicals present in the cavities is obtained if the adhesive layerconsists of a mixture of 30-70% by weight of polyisobutylene having anaverage molecular weight of 70,000 to 100,000 and 70-30% by weight ofpolyisobutylene having an average molecular weight of 1,000,000 to3,500,000. It is preferred that said mixture should consist ofpractically equal parts by weight of the respective constituents.

The adhesion between carrier layer and pressure-sensitive adhesive canstill be further improved in various ways. Such improvement is obtainedif the carrier layer consists of aluminum foil having an etched surface.Improvement of the adhesive strength can also be realized by making useof a carrier layer of aluminum foil coated with a polyisobutylenesurface layer applied from a solution in an organic solvent.

The adhesion between carrier layer and pressure-sensitive adhesive canstill be further improved in various ways. Such improvement is obtainedif the carrier layer consists of aluminum foil having an etched surface.Improvement of the adhesive strength can also be realized by making useof a carrier layer of aluminum foil coated with a polyisobutylenesurface layer applied from a solution in an organic solvent.

As example of a suitable solvent hexane may be mentioned. It ispreferred that such a surface layer should have a thickness of 2-10micrometers. It is preferred that the polyisobutylene used for such asurface layer should have an average molecular weight in the range of2,000,000 to 3,500,000.

The use of a carrier layer having a surface thus modified makes itpossible to obtain good adhesive strength also when employingpolyisobutylene having a relatively high molecular weight. A carrierlayer coated with a surface layer of polyisobutylene is thereforepreferably used if the carrier layer is bonded to the transparent coverlayer by means of a pressure-sensitive adhesive layer of polyisobutylenehaving an average molecular weight in the range of 2,000,000 to3,500,000.

The pressure-sensitive adhesive to be used according to the inventioncan be applied as thin layer to one side of the film material used astransparent cover layer, for instance polyester film. This may be donefrom a solution in, for instance, hexane or from the melt. The thicknessof the adhesive layer thus formed is as a rule 10-100 micrometers andpreferably 20-60 micrometers.

The polyisobutylene-coated side of the transparent cover layer isbrought into contact with the carrier layer on the side where thecavities to be closed off are positioned, and bonded to it underpressure without the temperature being increased. The bonding pressureapplied is generally in the range of 1 to 50 kg/cm².

Various types of polyisobutylene are suitable to be used for thispurpose. It is preferred that the average molecular weight of thepolyisobutylene should be in the range of 50,000 to 5,000,000. Byaverage molecular weight is to be understood the viscosity averagemolecular weight. This is calculated from the intrinsic viscosity, whichin its turn is determined from the rate of flow of a solution having aconcentration of 1 g/dl in isoctane through the capillary of anUbbelohde viscometer at a temperature of 20° C.

For the calculation, the following formula is used: ##EQU1## where:

[n]=intrinsic viscosity

n_(sp) =t/t-1=specific viscosity

t=rate of flow of the solution, corrected in accordance withHagenbach-Couette

t_(o) =rate of flow of the solvent, corrected in accordance withHagenbach-Couette

c=concentration of the solution in g/dl

M_(v) =average molecular weight

The polyisobutylene used has a good resistance to the chemicalsubstances present in the cavities, does not influence their meltingpoint, and hardly absorbs chemical substances and does not allow thepassage thereof.

In FIG. 17 the cover layer 66 is bonded to the carrier layer 67 by anadhesive layer 68. This adhesive layer 68 consists of apressure-sensitive adhesive which is entirely or substantially ofpolyisobutylene and can be applied to the carrier layer 67 without themelt temperature of the temperature-sensitive composition 69 in thecavities being exceeded.

In FIG. 18 the carrier layer 67 is still provided with a surface layer70 of polyisobutylene. The latter serves to improve the adhesion betweenthe pressure-sensitive polyisobutylne of the adhesive layer 68,consisting essentially of polyisobutylene, and the material of thecarrier layer 67. The surface layer 70 is generally obtained byproviding the carrier layer material with a thin coat of a solution ofpolyisobutylene in an organic solvent, e.g. hexane, and subsequentlyallowing the solvent to evaporate. The temperature-sensitive composition69 in FIGS. 17 and 18 is preferably selected from the novel compositionsof matter of this invention. When the temperature-sensitive composition69 is a classical composition of matter it is used together with anindicator means (not shown in FIGS. 17 and 18), which may be anyindicator means known in the art, e.g. a layer of paint located at thebottom of the cavity, a dye dispersed in the temperature-sensitivecomposition or an indicator layer of absorbent material located abovethe temperature-sensitive composition.

Although the invention has been described with reference to specificembodiments above, numerous variations and modifications will becomeevident to those skilled in the art, without departing from the scopeand spirit of the invention as described above defined in the appendedclaims, and as shown in the following examples:

EXAMPLE 1

About 1.25 grams of pinacyanol iodide was mixed and dissolved in a 100ml beaker by mechanical stirring means in a solvent system of 24.99 g ofa mixture of ortho-bromonitrobenzene and ortho-chloronitrobenzene (75%of the solvent system was composed of ortho-bromonitro- benzene and 25%was composed of ortho-chloronitrobenzene). The 0.05% pinacyanol iodidecontent could be determined accurately by means of a Mettler™ balancewherein 0.0125 g of pinacyanol iodide was placed on top of paperweighing 0.2426 g to obtain the objective of a total 0.2551 g. Thepinacyanol iodide was mixed in the beaker with the 24.99 g ofortho-bromonitrobenzene: ortho- chloronitrobenzene solution at fromabout 45° C. to about 60° C. to obtain a uniform novel composition ofmatter. This liquid was allowed to cool, and at about 38.04° C. withartificial nucleation the liquid solution changed from a blue color to asolid solution which was light brown rose. This example demonstratesthat a novel composition of matter employing a Group III compound ofpinacyanol iodide without the presence of a Group I or Group II compoundmay alone change color in a transition from a liquid to a solid state.It was found that upon heating up the solid solution back into theliquid phase, that the solution turned from a light brown back to itsoriginal blue form.

EXAMPLE 2

In the same manner as Example 1, a 10.0 g solution of 0.05% chlorophenolblue (a Group I and Group III material) and ethyl red (a Group IImaterial), wherein the chlorophenol blue weighed 0.00375 g and the ethylred weighed 0.00125 g, were added to a liquid solution ofortho-bromonitrobenzene:ortho-chloronitrobenzene of 9.995 g, wherein theratio of the ortho-bromonitrobenzene to the ortho-chloronitrobenzene inthe 9.995 g solvent system was 3:1 by weight. The 0.00375 g ofchlorophenol blue and 0.00125 g of ethyl red were added simultaneouslyto the ortho-bromonitrobenzene:ortho-chloronitrobenzene solution at fromabout 40° C. to about 60° C. The liquid solution had a red color thatchanged at about 37.5° C. to a yellow-orange color in the solid stateimmediately at the change in state. Upon heating, the yellow solidsolution turned at 38.04° C. back to its original red color. Thisexample demonstrates that a combination of a Group I compound and aGroup II compound for a novel composition of matter in a suitable weaklypolar aromatic solvent system will change color upon a correspondingchange from a liquid to a solid state or vice versa.

EXAMPLE 3

In the same manner as Example 1, a 0.05% solution of ethyl red (a GroupII compound) consisting of 0.005 g of ethyl red was mixed at from about40° C. to about 60° C. in a solution composed of 75%ortho-bromonitrobenzene and 25% ortho-chloronitrobenzene wherein theortho-bromonitrobenzene and ortho-chloronitrobenzene weighed a total of9.995 g. No Group I material was added to the instant solution. Theliquid at 40° C. was purple in color, but upon solidifying at 38.04° C.with the aid of artificial nucleation remained in its original purpleform for several days. Likewise, upon reheating, the purple solidsolution turned back into a purple liquid at 38.04° C. This exampledemonstrates that a Group II material in and of itself without thepresence of a Group III material will not undergo the desired colorchange without a Group I material with the corresponding change inphases, and therefore, a Group II material alone will not suffice forone of our novel compositions of matter. (One notes that the phenomenaobserved herein is inconsistent with the complement of the theoryproposed by R. B. McKay and P. J. Hillson, "Methachromatic Behavior ofDyes in Solution", 61 TRANSACTIONS OF FARADAY SOCIETY 1800 (1965).

EXAMPLE 4

In this example, in the same manner as Example 1, a solution of 0.05%bromochlorophenol blue and pinacyanol chloride (a Group II/Group IIIcompound) mixture where the ratio of bromochloro-phenol blue topinacyanol chloride was 5:1 (0.0042 g bromochloro-phenol blue wasemployed to 0.0008 g pinacyanol chloride with 9.9995 g of a solventsolution composed of 75% ortho-bromonitro-benzene and 25%ortho-chloronitrobenzene). Again, by the use of a Mettler™ balance, theweight of the bromochlorophenol blue and pinacyanol chloride could beaccurately determined after placing these materials on pieces of paperweighing 0.2517 g and 0.2457 g, respectively. The 0.0042 gbromochlorophenol blue and 0.0008 g pinacyanol chloride was added atfrom 40° C. to 60° C. to theortho-bromonitrobenzene:ortho-chloronitrobenzene solution in a 100 mlbeaker and stirred by mechanical stirring means. The greenish-blueliquid solution was allowed to cool from 40° C. to its solidificationpoint at about 38.04° C., whereby it changed with the aid of artificialnucleation instantly to a yellowish-green solid form. This exampledemonstrates clearly that another Group I compound, bromochlorophenolblue, is suitable for use in the making of a novel composition of matterwhen taken into a solvent mixture with a Group II/Group III compound,pinacyanol chloride, and will change color upon a corresponding changein state.

EXAMPLE 5

In the same manner as the preceding Examples, a 10 g solution of 0.05%by weight bromochlorophenol blue (0.005 g by Mettler™ balance) was addedto a 25:75 weight ratio ortho-chloronitrobenzene:ortho-bromonitrobenzeneof 9.995 g, at a temperature from about 40° C. to about 60° C. Theliquid solution at 40° C. was yellow, and was allowed to cool slowly toits solidification point at about 38.04° C. Upon solidification, thematerial remained yellow in its solid state. Upon reheating, there wasno change in color visible to the naked eye. This example demonstratesthat a Group I compound taken alone without a Group II or III compoundwill not bring forth the desired color change results at the change inphases from a liquid state to a solid state.

EXAMPLE 6

A solution of about 0.05 mass % of chlorophenol red in dibenzofurane wasprepared by adding the chlorophenol red to liquid dibenzofurane at 95°C. After dissolution of the chlorophenol red a yellow liquid wasobtained. After this liquid had been cooled to about 87° C., it began tosolidify and when the solidification was complete a red colored solidwas obtained. Upon heating the red solid, it changed back into a yellowliquid. This example demonstrates the use of a Group I and Group IIImember dissolved in a heterocyclic solvent to obtain a color changewhile passing from the liquid state to the solid state, or conversely.

EXAMPLE 7

In the same manner as Example I, a solution of 0.037 mass %naphthalenesulphonic acid and 0.013 mass % of ethyl violet was preparedin a mixture of ortho-bromo-nitrobenzene and ortho-chloronitrobenzene(mass ratio 3:1). Whereas the liquid solution was green, the solidsolution obtained by artificial nucleation at 38° C. was yellow. Uponheating the composition to its melting point a green liquid wasobtained. This example demonstrates that the combination of an acid withpK of less than about 2 and an amino-triphenylmethane dye will changecolor while passing from the liquid state to the solid state, orconversely.

EXAMPLE 8

This example demonstrates the use of a combination of a dye having amolecular structure containing a lactone group and an acid having a pKof about 8 to about 12. In the same way as described in Example 1, acomposition of matter was prepared by dissolving 0.05 mass % phenol in amixture of ortho-bromonitrobenzene and ortho-chloronitrobenzene (massratio 3:1). The liquid solution was yellow, and turned blue when it hadcompletely solidified at 37.5° C. by artificial nucleation. Upon heatingthe composition it became yellow again.

EXAMPLE 9

This example deals with a dye falling beyond the scope of thisinvention. In the same way as described in Example I, a solution wasprepared of Fast Blue Salt B in a mixture of ortho-bromonitrobenzene andortho-chloronitrobenzene (mass ratio 3:1). The color of the liquid wasyellow and did not change after complete crystallization of the solvent.

EXAMPLE 10

This example gives dyes tested for their suitability as a Group IIImember in various solvents at different concentrations. The results aregiven in Table 2.

Unless otherwise indicated, each of the cases 1-117 in the followingTable 2 employs a solvent system of 75 weight percentortho-chloronitro-benzene: 25 weight percent ortho-bromonitrobenzene,with about 0.05 weight percent of indicated Group I, Group II, Group IIIor other organic compounds. The solution of each case was prepared in asimilar manner as Example 1.

                                      TABLE 2                                     __________________________________________________________________________                                        Concentration                                                                         Color                             No. Class   Dye          Solvent    % (m/m) Liquid    Solid                   __________________________________________________________________________    1   nitroso dyes                                                                          Irgalith green BLN                                                                         OBNB/OCNB  0.05    *yellowish green                                                                        yellowish green                     (Ciba-Geigy) 3:1                                                  2   nitroso dyes                                                                          Naphtol green B                                                                            OBNB/OCNB  0.2     *green    green                               C.I. Acid green 1                                                                          3:1                                                              C.I. No. 10020          0.05    light green                                                                             light green                         (Baker)                 0.005   yellow    yellow                  3   nitroso dyes                                                                          1-nitroso-2-naphtol                                                                        OBNB/OCNB  0.2     brown     brown                               C.I. Mordant green 4                                                                       3:1        0.05    yellowish brown                                                                         yellowish brown                     C.I. No. 10005          0.05    yellow    yellow                      (Fluka)                                                                   4   nitro dyes                                                                            Naphtol Yellow S                                                                           OBNB/OCNB  0.05    *yellow   yellow                              C.I. Acid yellow 1                                                                         3:1                                                              C.I. No. 10316                                                                (Eastman Kodak)                                                   5   nitro dyes                                                                            Artisil Yellow F-L                                                                         OBNB/OCNB  0.05    *yellow   yellow                              (Sandoz)     3:1                                                              C.I. Disperse                                                                 yellow 42                                                                     C.I. No. 10388                                                    6   nitro dyes                                                                            Aurantia     OBNB/OCNB  0.2     *red      dark orange                         C.I. No. 10360                                                                             3:1                                                              Fluka                                                             7   azo dyes                                                                              Savinyl red BLSN                                                                           OBNB/OCNB  0.05    red       red                                 (Sandoz)     3:1                                                              C.I. Solvent red 90                                               8   azo dyes                                                                              Savinyl Fire Red                                                                           OBNB/OCNB  0.05    red       red                                 3 GLS (Sandoz)                                                                             3:1                                                              C.I. Solvent red 124                                              9   azo dyes                                                                              Orasol Orange RLN                                                                          OBNB/OCNB  0.05    red       orange-red                          (Ciba-Geigy) 3:1                                                                           lauryl                                                                        alcohol                                              10  monoazo 4-(p-ethoxyphenyl-                                                                         OBNB/OCNB  0.2     brownish red                                                                            dark yellow                         azo)-m-phenylene                                                                           3:1        0.05    reddish orange                                                                          dark yellow                         diamine mono-           0.005   yellow    yellow                              hydrochloride                                                                              lauryl     0.2     *orange   orange                              (Eastman Kodak)                                                                            alcohol                                              11  monoazo Orasol navy blue                                                                           OBNB/OCNB  0.2     dark blue bluish black                        (Ciba-Geigy) 3:1        0.05    dark blue greenish blue                       C.I. Solvent blue 53    0.005   bluish green                                                                            green                                            formamide  0.2     dark blue dark blue                                                   0.05    dark blue dark blue                                                   0.005   blue      blue                                             lauryl     0.2     dark blue dark blue                                        alcohol    0.05    dark blue blue                                                        0.005   blue      light blue              12  monoazo Organol Orange                                                                             OBNB/OCNB  0.2     reddish orange                                                                          reddish orange                      (Ugine Kuhlmann)                                                                           3:1        0.05    orange    orange                              C.I. Solvent orange 2   0.005   orange    orange                              C.I. No. 12100                                                                             formamide  0.2     *dark orange                                                                            orange                                           lauryl     0.2     dark orange                                                                             dark orange                                      alcohol    0.05    orange    orange                                                      0.005   orange    light orange            13  monoazo Janus Green  OBNB/OCNB  0.2     dark blue dark blue                           C.I. No. 11050                                                                             3:1        0.05    dark blue green                               (B.D.H.)                0.005   green     green                                            formamide  0.2     dark blue dark blue                                                   0.05    dark blue dark blue                                                   0.005   blue      blue                                             lauryl     0.2     dark blue blue                                             alcohol    0.05    blue      light blue                                                  0.005   light blue                                                                              nearly colorless        14  monoazo Irgalith Red PR                                                                            OBNB/OCNB  0.2     orange-red                                                                              red                                 (Ciba-Geigy) 3:1        0.05    dark orange                                                                             pink                                C.I. Pigment red 3      0.005   orange    orange-yellow                       C.I. No. 12120                                                                             formamide  0.2     *red      red                     15  monoazo Azophloxin   OBNB/OCNB  0.2     dark red  dark red                            C.I. Acid red 1                                                                            3:1        0.05    reddish brown                                                                           reddish brown                       Food red 10             0.005   yellow    yellow                              C.I. No. 18050                                                                (Fluka)                                                           16  monoazo Dimethyl Yellow                                                                            OBNB/OCNB  0.2     reddish orange                                                                          orange                              C.I. Solvent yellow 2                                                                      3:1        0.05    orange    orange                              C.I. No. 11020          0.005   orange    dark yellow                         (A.C.F.)                                                                                   lauryl     0.2     yellowish orange                                                                        dark yellow                                      alcohol    0.05    dark yellow                                                                             yellow                                                      0.005   yellow    light yellow                                     naphthalene                                                                              0.05    orange    dark yellow             17  monoazo Fast Yellow  OBNB/OCNB  0.2     orange    dark yellow                         C.I. Acid yellow 9                                                                         3:1        0.05    dark yellow                                                                             yellow                              Food yellow 2           0.005   yellow    yellow                              C.I. No. 13015                                                                (Merck)      lauryl     0.2     *orange   yellow                                           alcohol                                              18  monoazo Methyl Red,  OBNB/OCNB  0.2     red       red                                 sodium salt  3:1        0.05    red       orange-brown                        C.I. Acid red 2         0.005   dark orange                                                                             orange                              C.I. No. 13020                                                                (Merck)      lauryl     0.2     reddish orange                                                                          orange-yellow                                    alcohol    0.05    reddish orange                                                                          light brown                                                 0.005   orange    light orange                                     naphthalene                                                                              0.05    orange    orange                  19  monoazo Alizarin Yellow R                                                                          OBNB/OCNB  0.2     *greenish brown                                                                         brownish yellow                     C.I. Mordant orange 1                                                                      3:1                                                              C.I. No. 14030                                                                (Merck)                                                           20  monoazo Eriochrome Black T                                                                         OBNB/OCNB  0.2     *dark brown                                                                             brown                               C.I. Mordant black 11                                                                      3:1                                                              C.I. No. 14645                                                                (Baker)                                                           21  monoazo Chromotope 2R                                                                              OBNB/OCNB  0.2     *green    light green                         C.I. Acid red 29                                                                           3:1                                                              Mordant blue 80                                                               C.I. No. 16570                                                                (H. & W.)                                                         22  monoazo Ponceau 6R   OBNB/OCNB  0.2     *dark brown                                                                             yellowish brown                     C.I. Food red 8                                                                            3:1                                                              C.I. No. 16920                                                                (Merck)                                                           23  monoazo Titan yellow OBNB/OCNB  0.2     yellow    yellow                              C.I. Direct yellow 9                                                                       3:1        0.05    yellow    yellow                              C.I. No. 19540          0.005   yellow    yellow                              (B.D.H.)                                                          24  monoazo Yellow orange S                                                                            OBNB/OCNB  0.2     red       orange                              C.I. Food yellow 3                                                                         3:1        0.05    orange    dark yellow                         C.I. No. 15985          0.005   yellow    yellow                              (Merck)                                                           25  monoazo Brilliant Ponceau 5R                                                                       OBNB/OCNB  0.2     *brownish red                                                                           light brown                         C.I. Acid red 18                                                                           3:1        0.05    brownish yellow                                                                         brownish yellow                     Food red 7              0.005   yellow    yellow                              C.I. No. 16225                                                                (Holliday)                                                        26  monoazo Chrysoidin G OBNB/OCNB  0.2     red       ochre                               C.I. Basic orange 2                                                                        3:1        0.05    reddish orange                                                                          dark yellow                         C.I. No. 11270          0.005   dark yellow                                                                             light yellow                        (Fluka)                                                                                    lauryl     0.2     red       red                                              alcohol    0.05    orange-red                                                                              reddish orange                                              0.005   dark yellow                                                                             yellow                                           naphthalene                                                                              0.05    orange    orange                  27  monoazo Chrysoidin R OBNB/OCNB  0.2     *dark orange-red                                                                        dark orange-red                     C.I. Basic orange 1                                                                        3:1                                                              C.I. No. 11320                                                                (Fluka)                                                           28  monoazo Eriochrome Black A                                                                         OBNB/OCNB  0.2     black     dark green                          C.I. Mordant black 1                                                                       3:1        0.05    moss green                                                                              moss green                          C.I. No. 15710          0.005   light green                                                                             light green                         (M.C. & B.)                                                       29  monoazo Benzyl orange                                                                              OBNB/OCNB  0.05    deep yellow                                                                             yellow                              (Merck)      3:1                                                                           lauryl     0.05    orange    yellow                                           alcohol                                                                       naphthalene                                                                              0.05    light orange                                                                            colorless               30  monoazo Ponceau G,R,2R                                                                             OBNB/OCNB  0.2     *brownish red                                                                           brownish yellow                     C.I. Acid red 26                                                                           3:1                                                              Food red 5                                                                    C.I. No. 16150                                                                (M.C. & B.)                                                       31  monoazo Chromolan Yellow                                                                           OBNB/OCNB  0.2     *light brown                                                                            yellow                              C.I. Acid yellow 54                                                                        3:1        0.05    yellow    yellow                              C.I. No. 19101          0.005   yellow    yellow                              (M.C. & B.)                                                       32  disazo  Fat Red BS (Sandox)                                                                        OBNB/OCNB  0.22    dark red  dark red                            C.I. Solvent red 24                                                                        3:1        0.05    dark red  brownish red                        C.I. No. 26105          0.005   light red light red                                        lauryl                                                                        alcohol    0.05    dark red  red                     33  disazo  Sudan Red B  OBNB/OCNB  0.2     dark red  dark red                            C.I. Solvent red 25                                                                        3:1        0.05    dark red  dark red                            C.I. No. 26110          0.005   red       orange                              (Fluka)                                                                                    lauryl                                                                        alcohol    0.2     *dark red dark red                                                    0.05    red       red                                                         0.005   light red light red                                        naphthalene                                                                              0.05    vermilion dark red                34  disazo  Bismark Brown G                                                                            OBNB/OCNB  0.2     very dark green                                                                         dark green                          C.I. Basic brown 1                                                                         3:1        0.05    brownish green                                                                          dark green                          C.I. No. 21000          0.005   light green                                                                             light green                         (Fluka)      lauryl                                                                        alcohol    0.2     *dark green                                                                             dark green                                       naphthalene                                                                              0.05    yellow    light brown             35  disazo  Fat Black    OBNB/OCNB  0.2     black     black                               C.I. Solvent black 3                                                                       3:1        0.05    black     black                               C.I. No. 26150          0.005   very dark green                                                                         dark green                          (Fluka)                 0.0005  green     light green                                      lauryl     0.2     black     black                                            alcohol    0.05    black     dark blue                                                   0.005   dark blue blue                                                        0.0005  blue      light blue              36  disazo  Resorcin Brown                                                                             OBNB/OCNB  0.2     *brownish red                                                                           reddish brown                       C.I. Acid Orange 24                                                                        3:1        0.05    brownish yellow                                                                         brownish yellow                     C.I. No. 20170          0.005   yellow    yellow                              (M.C. & B.)                                                       37  disazo  Benzo Fast Pink 2BL                                                                        OBNB/OCNB  0.2     *green    light green                         C.I. Direct red 75                                                                         3:1                                                              C.I. No. 25380                                                                (M.C. & B.)                                                       38  disazo  Oil Red EGN  OBNB/OCNB  0.2     vermillion                                                                              dark red                            C.I. Solvent red 26                                                                        3:1        0.05    vermillion                                                                              dark red                            C.I. No. 16120          0.005   red       red                                 (M.C. & B.)                                                       39  disazo  Trypan Blue  OBNB/OCNB  0.2     light green                                                                             light green                         C.I. Direct blue 14                                                                        3:1        0.05    light green                                                                             light green                         C.I. No. 23850          0.005   light green                                                                             light green                         (Merck)                                                           40  disazo  Brillant Yellow                                                                            OBNB/OCNB  0.2     orange    orange                              C.I. Direct yellow 4                                                                       3:1        0.05    dark yellow                                                                             dark yellow                         C.I. No. 24890          0.005   yellow    yellow                  41  trisazo Chlorazol Black E                                                                          OBNB/OCNB  0.05    *greenish yellow                                                                        greenish yellow                     C.I. Direct black 38                                                                       3:1                                                              C.I. No. 30235                                                                (Eastman Kodak)                                                   42  trisazo Diamingreen B                                                                              OBNB/OCNB  0.2     green     light green                         C.I. Direct green 6                                                                        3:1        0.05    light green                                                                             light green                         C.I. No. 30295          0.005   yellowish green                                                                         yellowish green                     (Merck)                                                                                    lauryl                                                                        alcohol    0.2     *green    light green             43  trisazo Direct Green G                                                                             OBNB/OCNB  0.2     *green    light green                         C.I. Direct green 8     0.05    light green                                                                             light green                         C.I. No. 30315          0.005   yellow    yellow                              (M.C. & B.)                                                       44  azoic   Fast Red Salt 3 GL                                                                         OBNB/OCNB  0.2     yellowish orange                                                                        dark yellow                         C.I. No. 37040                                                                             3:1        0.05    very dark yellow                                                                        dark yellow                                                 0.005   yellow    yellow                  45  azoic   Fast Blue Salt BB                                                                          OBNB/OCNB  0.2     brownish yellow                                                                         greenish yellow                     C.I. No. 37175                                                                             3:1        0.05    brownish yellow                                                                         greenish yellow                     (Fluka)                 0.005   yellow    yellow                  46  azoic   Fast Garnet Salt GBC                                                                       OBNB/OCNB  0.2     dark brown                                                                              dark brown                          C.I. No. 37210                                                                             3:1        0.05    brownish red                                                                            brownish yellow                     (Fluka)                 0.005   yellow    yellow                  47  azoic   Fast Blue Salt B                                                                           OBNB/OCNB  0.2     yellow    yellow                              C.I. No. 37235                                                                             3:1        0.05    yellow    yellow                              (Fluka)                 0.005   yellow    yellow                  48  stilbene                                                                              Carta Yellow G 180%                                                                        OBNB/OCNB  0.2     *brownish yellow                                                                        yellow                              (Sandoz)     3:1        0.05    yellow    yellow                              C.I. Direct yellow 11   0.005   yellow    yellow                              C.I. No. 40000                                                    49  Diphenyl-                                                                             Auramin      OBNB/OCNB  0.2     yellow    yellow                      methane C.I. Basic yellow 2                                                                        3:1        0.05    yellow    yellow                              C.I. No. 41000          0.005   yellow    yellow                              (Merck)                                                           50  triaryl-                                                                              Malachite Green                                                                            OBNB/OCNB  0.2     green     green                       methane C.I. Basic green 4                                                                         3:1        0.05    green     green                               C.I. No. 42000          0.005   green     green                               (Y.W.Towers & Co.)                                                                         formamide  0.2     dark green                                                                              dark green                                                  0.05    green     green                                                       0.005   light green                                                                             light green             51  triaryl-                                                                              Brilliant Green                                                                            OBNB/OCNB  0.2     green     green                       methane C.I. Basic green 1                                                                         3:1        0.05    green     green                               C.I. No. 42020          0.005   green     green                               (Fluka)                                                                                    formamide  0.2     dark green                                                                              dark green                                                  0.05    green     green                                                       0.005   light green                                                                             light green             52  triaryl-                                                                              Methyl Violet                                                                              OBNB/OCNB  0.2     violet    violet                      methane C.I. Basic violet 1                                                                        3:1        0.05    bluish violet                                                                           bluish violet                       C.I. No. 42535          0.005   bluish violet                                                                           bluish violet                       (A.C.F.)                                                                                   formamide  0.2     violet    violet                                                      0.05    violet    violet                                                      0.005   violet    violet                  53  triaryl Xylene Cyanol FF                                                                           OBNB/OCNB  0.2     blue      blue                        methane C.I. No. 43535                                                                             3:1        0.05    blue      light blue                          (Baker)                 0.005   green     light green                                      formamide  0.2     blue      dark blue                                                   0.05    blue      blue                                                        0.005   blue      blue                    54  triaryl-                                                                              Erioglaucine OBNB/OCNB  0.2     blue      greenish blue               methane C.I. Acid blue 9                                                                           3:1        0.05    blue      green                               Food blue 2             0.005   green     light green                         C.I. No. 42090                                                                (B.D.H.)     lauryl     0.2     blue      light blue                                       alcohol    0.05    light blue                                                                              light blue                                                  0.005   light blue                                                                              light blue                                       naphthalene                                                                              0.05    greenish blue                                                                           greenish blue           55  triaryl-                                                                              Fuchsin BN   OBNB/OCNB  0.2     dark red  dark red                    methane C.I. Basic violet 2                                                                        3:1        0.05    dark red  reddish brown                       C.I. No. 42520          0.005   pinkish violet                                                                          greenish yellow                     (Merck)                                                                                    lauryl     0.2     dark purple                                                                             dark purple                                      alcohol    0.05    pinkish purple                                                                          purple                                                      0.005   pink      pink                                             napthtalene                                                                              0.05    *purple   lt. purple violet       56  triaryl-                                                                              Fuchsin      OBNB/OCNB  0.2     dark reddish                                                                            dark violet                 methane C.I. Basic violet 14                                                                       3:1                violet                                        C.I. No. 42510          0.05    dark red  brownish red                        (Merck)                 0.005   pinkish violet                                                                          greenish beige                                   lauryl     0.2     dark purple                                                                             dark purple                                      alcohol    0.05    purple    purple                                                      0.005   pink      pink                                             naphthalene                                                                              0.05    *red      light brown             57  triaryl-                                                                              Parafuchsin  OBNB/OCNB  0.2     dark red  dark brown                  methane C.I. Basic red 9                                                                           3:1        0.05    red       light brown                         C.I. No. 42500          0.005   light red orange-yellow                       (Fluka)                                                                                    lauryl     0.2     red       red                                              alcohol    0.05    purple-red                                                                              lilac purple                                                0.005   lilac     lilac                                            naphthalene                                                                              0.05    *dark purple                                                                            light purple            58  triaryl-                                                                              Aurintricarboxylic                                                                         OBNB/OCNB  0.2     *reddish orange                                                                         orange brown                methane acid, ammonium salt                                                                        3:1                                                              C.I. Mordant violet 39                                                        C.I. No. 43810                                                                (Merck)                                                           59  triaryl-                                                                              Patent Blue  OBNB/OCNB  0.2     very dark blue                                                                          dark blue                   methane C.I. Acid blue 1                                                                           3:1        0.05    dark blue bluish green                        Food blue 3             0.005   green     light green                         C.I. No. 42045                                                                (M.C. & B.)                                                       60  triaryl-                                                                              Ethyl Violet OBNB/OCNB  0.2     dark blue dark blue                           C.I. Basic violet 4                                                                        3:1        0.05    blue      blue                                C.I. No. 42600          0.005   blue      blue                                (M.C. & B.)                                                       61  triaryl-                                                                              Victoria Blue R                                                                            OBNB/OCNB  0.2     dark blue dk. greenish blue           methane C.I. Basic blue 11                                                                         3:1        0.05    dark blue dk. bluish green                    C.I. No. 44040          0.005   dark blue bluish green                        (M.C. & B.)                                                       62  triaryl-                                                                              Irgalith Violet MNC                                                                        OBNB/OCNB  0.2     bluish violet                                                                           bluish violet               methane (Ciba-Geigy) 3:1        0.05    blue      blue                                C.I. Pigment violet 3   0.005   blue      blue                                C.I. No. 42535: 2                                                                          formamide  0.2     bluish violet                                                                           violet                                                      0.05    bluish violet                                                                           bluish violet                                               0.005   bluish violet                                                                           bluish violet           63  triaryl-                                                                              Crystal Violet                                                                             OBNB/OCNB  0.2     bluish violet                                                                           violet                      methane C.I. Basic violet 3                                                                        3:1        0.05    blue      bluish violet                       C.I. No. 42555          0.005   blue      bluish violet                       (A.C.F.)                                                                                   formamide  0.2     violet    violet                                                      0.05    violet    bluish violet                                               0.005   violet    bluish violet           64  triaryl-                                                                              Irgalith Blue TNC                                                                          OBNB/OCNB  0.2     blue      blue                        methane (Ciba-Geigy) 3:1        0.05    blue      blue                                C.I. Pigment blue 1     0.005   blue      bluish green                        C.I. No. 42595: 2                                                                          formamide  0.2     blue      blue                                                        0.05    blue      blue                                                        0.005   blue      blue                    65  Xanthene                                                                              Phloxin B    OBNB/OCNB  0.2     orange    pinkish orange                      C.I. Acid Red 92                                                                           3:1        0.05    yellowish orange                                                                        yellowish orange                    C.I. No. 45410          0.005   yellow    yellow                                           formamide  0.2     orange-red                                                                              orange-red                                                  0.05    reddish orange                                                                          orange-brown-red                                            0.005   pink      pink                                             lauryl                                                                        alcohol    0.05    pink      light pink              66  Xanthene                                                                              Fluorescein, OBNB/OCNB  insoluble                                             sodium salt  3:1                                                              C.I. Acid yellow 73                                                                        formamide  0.2     yellow    orange-yellow                       C.I. No. 45350          0.05    yellow    yellow                              (Merck)                 0.005   yellow    yellow                                           lauryl                                                                        alcohol    0.05    *yellow   yellow                  67  Xanthene                                                                              Rose Bengale OBNB/OCNB  insoluble                                             C.I. Acid red 94                                                                           3:1                                                              C.I. No. 45440                                                                (I.G. Farben)                                                                              formamide  0.2     dark red  dark red                                                    0.05    violet-red                                                                              violet-red                                                  0.005   pinkish violet                                                                          pinkish violet          68  Xanthene                                                                              Rhodamine B  OBNB/OCNB  0.2     red       violet                              C.I. Basic violet 10                                                                       3:1        0.05    pinkish red                                                                             violet                              C.I. No. 45170          0.005   pinkish red                                                                             violet-pink-red                     (Merck)      formamide  0.2     red       reddish violet                                              0.05    orange-red                                                                              pinkish red                                                 0.005   pinkish orange                                                                          pink                                             lauryl                                                                        alcohol    0.05    violet-red                                                                              pinkish violet                                   naphthalene                                                                              0.05    dark-purple-red                                                                         lilac                                                               (fluorescent)                     69  Xanthene                                                                              Rhodamine B Base                                                                           OBNB/OCNB  0.2     red       red                                 C.I. Solvent red 49                                                                        3:1        0.05    red       deep pink                           C.I. No. 45170: 1       0.005   light red pink                                (Baker)                                                           70  Xanthene                                                                              Rhodamine 6 G                                                                              OBNB/OCNB  0.2     red       violet-red                          C.I. Basic Red 1                                                                           3:1        0.05    red       reddish violet                      C.I. No. 45160          0.005   orange    pinkish red                         (Merck)                                                                                    formamide  0.2     orange-red                                                                              purple-red                                                  0.05    orange    orange-pink                                                 0.005   orange-pink                                                                             orange-pink                                      lauryl                                                                        alcohol    0.05    pinkish orange                                                                          pink                    71  Xanthene                                                                              Pyronin G    OBNB/OCNB  0.2     reddish brown                                                                           violet-brown                        C.I. NO. 45005          0.05    red       brown                               (Fluka)                 0.005   pink      pinkish red                                      formamide  0.2     red       reddish violet                                              0.05    greenish red                                                                            brownish red                                                0.005   pink      pink                                             lauryl                                                                        alcohol    0.05    pink      pinkish violet          72  Xanthene                                                                              Irgalith Magenta TCB                                                                       OBNB/OCNB  0.2     red       violet-red                          (Ciba-Geigy) 3:1        0.05    red       violet-red                          C.I. Pigment violet 2   0.005   red       pink                                C.I. No. 45175                                                                             formamide  0.2     reddish orange                                                                          violet-red                                                  0.05    orange    orange-pink                                                 0.005   orange-pink                                                                             pink                                             lauryl                                                                        alcohol    0.05    *orange-pink                                                                            light pink              73  Xanthene                                                                              Irgalith Pink TYNC                                                                         OBNC/OCNB  0.2     red       violet-red                          (Ciba-Geigy) 3:1        0.05    orange-red                                                                              red                                 C.I. Pigment red 81:1   0.005   orange    red                                 C.I. No. 45160: 2                                                                          formamide  0.2     orange    brownish red                                                0.05    yellowish orange                                                                        pinkish red                                                 0.005   pink      pink                                             lauryl                                                                        alcohol    0.05    *orange-pink                                                                            light pink              74  Xanthene                                                                              Eosin Scarlet                                                                              OBNB/OCNB  0.05    *yellow   yellow                              C.I. Acid red 91                                                                           3:1                                                              C.I. No. 45400                                                                             formamide  0.05    *pinkish orange                                                                         orange                              (Fluka)                                                                                    lauryl     0.05    *orange   orange-pink                                      alcohol                                              75  Xanthene                                                                              Eosin Yellowish                                                                            OBNB/OCNB  0.05    *yellow   yellow                              C.I. Acid red 87                                                                           3:1                                                              C.I. No. 45380                                                                             formamide  0.05    orange    orange                              (Fluka)                                                                                    lauryl                                                                        alcohol    0.05    orange    pinkish orange          76  Xanthene                                                                              Erythrosin, Extra                                                                          OBNB/OCNB  0.05    *yellow   yellow                              Bluish       3:1                                                              (Fluka)                                                                       C.I. Acid red 51                                                                           formamide  0.05    orange-pink                                                                             pinkish orange                      C.I. No. 45430                                                                             lauryl                                                                        alcohol    0.05    pinkish orange                                                                          pinkish red             77  Xanthene                                                                              4',5'-Dibromo-                                                                             OBNB/OCNB  0.05    yellow    orange                              fluorescein  3:1                                                              C.I. Acid orange 11                                                           C.I. No. 45370                                                                             formamide  0.05    orange-yellow                                                                           orange-yellow                       (Eastman Kodak)                                                                            lauryl                                                                        alcohol    0.05    orange-yellow                                                                           orange-yellow           78  Xanthene                                                                              Ethyl Eosin  OBNB/OCNB  0.05    *reddish orange                                                                         orange                              C.I. Solvent red 45                                                                        3:1                                                              C.I. No. 45386                                                                             formamide  0.05    pinkish orange                                                                          orange-pink                         (Eastman Kodak)                                                                            lauryl                                                                        alcohol    0.05    *orange-pink                                                                            pink                    79  Xanthene                                                                              Gallein      OBNB/OCNB  0.05    *yellowish brown                                                                        brown                               C.I. Mordant violet 25                                                                     3:1                                                              C.I. No. 45445                                                                (Eastman Kodak)                                                                            formamide  0.05    brownish orange                                                                         light brown                                      lauryl                                                                        alcohol    0.05    brownish orange                                                                         violet                  80  Xanthene                                                                              Phloxine     OBNB/OCNB  0.2     red       brownish red                        C.I. Acid red 98                                                                           3:1        0.05    deep brownish                                                                           brownish yellow                     C.I. No. 45405                  yellow                                        (Merck)                 0.005   yellow    yellow                  81  Xanthene                                                                              Erythrosin yellowish                                                                       OBNB/OCNB  0.2     *red      brownish red                        blend        3:1        0.05    brownish yellow                                                                         lt. brownish red                    C.I. Acid red 95        0.005   yellow    yellow                              C.I. No. 45425                                                                (M.C. & B.)                                                       82  Xanthene                                                                              Cyanosin B   OBNB/OCNB  0.2     orange    orange                              C.I. No. 45420                                                                             3:1        0.05    orange    orange                              (ICN-K & K)             0.005   light orange                                                                            yellowish               83  sulphone-                                                                             Cresol red   OCNB       0.05    yellow    red                         phthalein                                                                             (Merck)      dioxane    0.05    yellow    reddish orange                                   water      0.05    yellow    red (deep                                                                     cooling)                                         naphthalene                                                                              0.05    light yellow                                                                            red                     84  sulphone                                                                              chlorophenol red                                                                           OBNB/OCNB  0.05    yellow    red                         phthalein                                                                             (Merck)      3:1                                                                           OCNB       0.05    yellow    red                                              dioxane    0.05    yellow    reddish red                                      paraffin   0.05    nearly colorless                                                                        pink                                             para-                                                                         dichlorobenzene                                                                          0.05    pink      red                                              water      0.05    yellow    red (deep                                                                     cooling)                                         naphthalene                                                                              0.05    nearly colorless                                                                        red                                              o-iodonitrobenzene                                                                       0.05    brown     orange                                           m-iodonitrobenzene                                                                       0.05    yellow    red                                              p-iodonitrobenzene                                                                       0.05    brown     red                                              p-chloronitro-                                                                benzene    0.05    yellow    red                                              m-bromonitrobenzene                                                                      0.05    yellow    red                                              p-bromonitrobenzene                                                                      0.05    orange    red                                              p-dibromobenzene                                                                         0.05    pink      red                                              p toluic acid                                                                            0.05    yellow    red                                              2 naphtol  0.05    brown     red                                              indole     0.05    orange    reddish brown                                    dibenzofurane                                                                            0.05    yellow    red                     85  sulphone-                                                                             chlorophenol blue                                                                          OBNB/OCNB  0.05    yellow    yellowish-orange            phthalein                                                                             (Info-Chem)  3:1                                                  86  sulphone-                                                                             bromophenol blue                                                                           OBNB/OCNB  0.05    yellow    yellowish-orange            phthalein                                                                             (Baker)      3:1                                                  87  sulphone-                                                                             bromocresol purple                                                                         OBNB/OCNB  0.05    yellow    orange-yellow               phthalein                                                                             (Baker)      3:1                                                  88  sulphone-                                                                             chlorocresol green                                                                         OBNB/OCNB  0.05    yellow    yellowish-orange            phthalein                                                                             (Info-Chem)  3:1                                                  89  acridine                                                                              Acridine yellow                                                                            OBNB/OCNB  0.05    *yellow   yellow                              C.I. No. 46025                                                                             3:1                                                              (Eastman Kodak)                                                   90  acridine                                                                              Coriphosphine O                                                                            OBNB/OCNB  0.2     deep violet                                                                             brown                               C.I. Basic yellow 7                                                                        3:1        0.05    deep violet                                                                             greenish brown                      C.I. No. 46020          0.005   brown     greenish beige                      (ICN-K & K)                                                       91  acridine                                                                              Acriflavine  OBNB/OCNB  0.2     orange    dark yellow                         C.I. No. 46000                                                                             3:1        0.05    yellowish orange                                                                        yellow                              (ICN-K & K)             0.005   yellow    light yellow            92  acridine                                                                              Acridine Orange                                                                            OBNB/OCNB  0.05    brownish orange                                                                         brownish orange                     C.I. Basic orange 14                                                                       3:1                                                              C.I. No. 46005                                                                             OCNB       0.05    red       orange                                                      0.01    orange    yellow                              (Merck)                                                                                    lauryl                                                                        alcohol    0.05    yellowish orange                                                                        orange                  93  quinoline                                                                             Terasil Yellow 2GW                                                                         OBNB/OCNB  0.05    *yellow   yellow                              C.I. Disperse yellow 54                                                                    3:1                                                              C.I. No. 47020                                                                (Ciba-Geigy)                                                      94  quinoline                                                                             Quinoline Yellow                                                                           OBNB/OCNB  0.2     dark yellow                                                                             dark yellow                         C.I. Solvent yellow 33                                                                     3:1        0.05    yellow    yellow                              C.I. No. 47000          0.005   yellow    yellow                              (M.C. & B.)                                                       95  quinoline                                                                             Pinacyanol chloride                                                                        OCNB       0.05    blue      violet                              (Info-Chem)             0.005   blue      green                                            OBNB/OCNB 3:1                                                                            0.05    blue      violet-blue             96  quinoline                                                                             Pinacyanol bromide                                                                         OBNB/OCNB  0.05    blue      violet                              (Fluka)      3:1                                                  97  quinoline                                                                             Pinacyanol iodide                                                                          OBNB/OCNB  0.05    blue      lt. greenish pink                   (Info-Chem)  3:1                                                                           naphthalene                                                                              0.05    blue      light blue                                       n-tetracosane                                                                            0.025   light blue                                                                              light violet                                     dibenzofurane                                                                            0.05    blue      lt. bluish green                                 1-tetradecanol                                                                           0.05    blue      light violet                                                0.025   blue      light grey                                       stearic acid                                                                             0.025   blue      light greyish                                                                 violet                                           iodole     0.025   dark blue blue                    98  quinoline                                                                             Quinaldine Red                                                                             OBNB/OCNB  0.05    purple red                                                                              light purple                        (Merck)      3:1                                                                           naphthalene                                                                              0.05    deep purple-red                                                                         beige                   99  quinoline                                                                             Cryptocyanine                                                                              OBNB/OCNB  0.05    green     bluish green                                     3:1                                                                           p-dichloro-                                                                   benzene    0.05    light blue                                                                              nearly colorless                                 naphthalene                                                                              0.05    green     dark blue                                        OCNB       0.05    dark green                                                                              bluish green            100 quinoline                                                                             1,1'-Diethyl-2,2'-                                                                         OBNB/OCNB  0.05    red       brownish yellow                     cyanine iodide                                                                             3:1                                                              (Eastman Kodak)                                                                            naphthalene                                                                              0.05    deep red  reddish pink                                     OCNB       0.05    deep reddish                                                                            red                     101 quinoline                                                                             2-(p-dimethylamino-                                                                        OBNB/OCNB  0.05    red       orange                              atyryl-1-ethyl-                                                                            3:1                                                              pyridinium iodide                                                                          naphthalene                                                                              0.05    red       orange                              (Eastman Kodak)                                                                            OCNB       0.05    red       orange                  102 quinoline                                                                             3,3'-Diethylthia-                                                                          OBNB/OCNB  0.05    bluish green                                                                            blue                                dicarbocyanine                                                                             3:1                                                              iodide                                                                        (Eastman Kodak)                                                   103 quinoline                                                                             Ethyl Red    OBNB/OCNB  0.05    red       red*.sup.2                          (Eastman Kodak)                                                                            3:1                                                                           p-dichlorobenzene                                                                        0.05    violet    light violet            104 quinoline                                                                             Dicyanine A  OBNB/OCNB  0.05    green     blue green                          (Eastman Kodak)                                                                            3:1                                                  105 quinoline                                                                             Merocyanine 540                                                                            OBNB/OCNB  0.05    purple    rose                                (Eastman Kodak)                                                                            3:1                                                  106 quinoline                                                                             Neocyanine   OBNB/OCNB  0.05    green     yellow green                        (Eastman Kodak)                                                                            3:1                                                  107 thiazole                                                                              Thioflavine TCN                                                                            OBNB/OCNB  0.2     *yellow   yellow                              C.I. Basic yellow 1                                                                        3:1                                                              C.I. No. 49005 (Merck)                                            108 azine   Neutral Red (chloride)                                                                     OBNB/OCNB  0.2     red       reddish brown                       C.I. Basic red 5                                                                           3:1        0.05    red       reddish orange                      C.I. No. 50040          0.005   red       light orange                        (Baker)      formamide  0.2     red       dark brown                                                  0.05    orange-red                                                                              reddish brown                                               0.005   orange    yellow orange                                    lauryl     0.2     red       brown                                            alcohol    0.05    red       reddish orange                                              0.005   reddish orange                                                                          pink                                             naphthalene                                                                              0.05    red       dark brown              109 azine   Neutral Red (iodide)                                                                       OBNB/OCNB  0.05    deep red  reddish brown                       (ICN-K&K)    3:1        0.005   red       brownish orange         110 azine   Nigrosine    OBNB/OCNB  0.2     dark grey-blue                                                                          dark grey-black                     C.I. Acid black 2                                                                          3:1        0.05    blue      grey blue                           C.I. No. 50420          0.005   greenish  greenish                            (Edward Gurr)                                                                              formamide  0.2     dark violet                                                                             dk. violet-black                                            0.05    dark violet                                                                             dark violet                                                 0.005   violet    violet                                           lauryl     0.2     grey-blue-violet                                                                        dark violet                                      alcohol    0.05    blue-violet                                                                             violet                                                      0.005   violet    violet                  111 azine   Savinyl Blue B                                                                             OBNB/OCNB  0.2     dark blue dark blue                           (Sandoz)     3:1        0.05    blue      light blue                          C.I. Acid blue 59       0.005   greenish blue                                                                           green                               C.I. No. 50315                                                                             formamide  0.2     dark blue dark blue                                                   0.05    dark blue dark blue                                                   0.005   blue      blue                                             lauryl     0.2     dark blue blue                                             alcohol    0.05    dark blue blue                                                        0.005   blue      light blue              112 azine   Orasol Blue BLN                                                                            OBNB/OCNB  0.2     dark blue dark blue                           (Ciba-Geigy) 3:1        0.05    blue      blue                                C.I. Solvent blue 49    0.005   greenish blue                                                                           greenish blue                                    formamide  0.2     dark blue dark blue                                                   0.05    dark blue dark blue                                                   0.005   blue      blue                                             lauryl     0.2     dark blue dark blue                                        alcohol    0.05    blue      blue                                                        0.005   light blue                                                                              blue                    113 azine   Safranin O   OBNB/OCNB  0.05    *red      brownish red                        C.I. No. 50240                                                                             3:1        0.005   *orange   light brown                         (Merck)                                                                                    formamide  0.05    red       red                                              lauryl     0.05    red       orange-brown                                     alcohol    0.005   pinkish red                                                                             pink                    114 azine   Azocarmin G  OBNB/OCNB  0.05    *yellow   brownish yellow                     C.I. Acid red 101                                                                          3:1                                                              C.I. No. 50085                                                                             formamide  0.05    violet red                                                                              violet red                          (Fluka)                                                                                    lauryl                                                                        alcohol    0.05    *violet pink                                                                            violet pink             115 azine   Azocarmine BX (B)                                                                          OBNB/OCNB  0.2     red       red                                 C.I. Acid red 103                                                                          3:1        0.05    red       beige                               C.I. No. 50090          0.005   yellow    yellow                              (Merck)      lauryl                                                                        alcohol    0.2     red       pink                                                        0.05    purple    light purple                                                0.005   pink      pink                                             naphthalene                                                                              0.05    dark red  red                     116 azine   Phenosafranine                                                                             OBNB/OCNB  0.2     dark red  dark red                            C.I. No. 50200                                                                             3:1        0.05    red       beige                               (Baker)                 0.005   yellow    yellow                                           lauryl     0.2     dark red  purple red                                       alcohol    0.05    dark pink dark pink                                                   0.005   pink      pink                                             naphthalene                                                                              0.05    pink      pink                    117 azine   Rhoduline Violet                                                                           OBNB/OCNB  0.2     violet    dp reddish violet                   C.I. No. 50215                                                                             3:1        0.05    violet    reddish violet                      (ICN-K&K)               0.005   red       violet red              118 oxazine Deorlene Blue 5G                                                                           OBNB/OCNB  0.05    bluish green                                                                            bluish green                        (Ciba)       3:1                                                              C.I. Basic blue 3                                                             C.I. No. 51004                                                    119 oxazine Solophenyl Brilliant                                                                       OBNB/OCNB  0.05    *yellow   greenish                            blue BL (Ciba-Geigy)                                                                       3:1                                                              C.I. Direct blue 106                                                                       formamide  0.05    dark blue dark blue                           C.I. No. 51300                                                    120 oxazine Nile Blue A  OBNB/OCNB  0.05    *greenish blue                                                                          grey-green-blue                     C.I. Basic blue 12                                                                         3:1                                                              C.I. No. 51180                                                                (Eastman Kodak)                                                   121 oxazine Gallocyanine OBNB/OCNB  0.2     dark blue dark green                          C.I. Mordant blue 10                                                                       3:1        0.05    bluish green                                                                            light green                         C.I. No. 51030          0.005   green     greenish yellow                     (ICN-K&K)                                                         122 oxazine Gallamine Blue                                                                             OBNB/OCNB  0.2     *greenish blue                                                                          light green                         C.I. Mordant blue 45                                                                       3:1                                                              C.I. No. 51045                                                                (ICN-K&K)                                                         123 oxazine Celestine Blue                                                                             OBNB/OCNB  0.2     blue      green                               C.I. Mordant blue 14                                                                       3:1        0.05    blue      light green                         C.I. No. 51505          0.005   green     greenish yellow                     (ICN-K&K)                                                         124 thiazine                                                                              Methylene Blue                                                                             OBNB/OCNB  0.2     dark blue dark violet                         C.I. Basic blue 9                                                                          3:1        0.05    dark blue blue                                C.I. No. 52015          0.005   green     greenish                            (Baker)                                                                                    formamide  0.2     dark blue dark blue                                                   0.05    dark blue dark blue                                                   0.005   blue      blue                                             lauryl     0.2     dark blue violet                                           alcohol    0.05    dark blue violet                                                      0.005   blue      blue                                             OCNB       0.05    deep blue violet                                                      0.01    green/blue                                                                              violet                  125 thiazine                                                                              Thionin (Lauth's                                                                           OBNB/OCNB  0.2     *dark red greenish violet                     violet)      3:1        0.05    dark red  greenish                            C.I. No. 52000          0.01    red       pink                                (Merck)                 0.005   red       beige                                            formamide  0.2     violet-blue                                                                             dark violet                                                 0.05    violet-blue                                                                             blue                                                        0.005   violet    blue                                             lauryl     0.2     dark violet                                                                             violet                                           alcohol    0.05    violet    violet                                                      0.005   pink-violet                                                                             violet                                           OCNB       0.05    deep red  violet                                                      0.01    wine red  pink                    126 thiazine                                                                              Toluidine Blue 0                                                                           OBNB/OCNB  0.2     dark blue bluish violet                       C.I. Basic blue 17                                                                         3:1        0.05    dark blue violet                              C.I. No. 52040          0.005   greenish blue                                                                           pink                                (Derva)                                                                                    OCNB       0.05    deep blue violet                                                      0.01    blue/green                                                                              pink/violet                                      t. butanol 0.01    blue      blue                                             formamide  0.2     dark blue blue violet                                                 0.05    dark blue dark blue                                                   0.005   blue      blue                                             lauryl     0.2     dark blue violet                                           alcohol    0.05    blue      violet                                                      0.005   light blue                                                                              nearly colorless                                 naphthalene                                                                              0.05    deep blue blue                    127 thiazine                                                                              Methylene Green                                                                            OBNB/OCNB  0.05    dk bluish green                                                                         dark green                          C.I. Basic green 5                                                                         3:1                                                              C.I. No. 52020                                                                (Fluka)      formamide  0.05    dk bluish green                                                                         dk bluish green                                  lauryl     0.05    *blue     grey                                             alcohol                                              128 thiazine                                                                              Azure, A,B,C OBNB/OCNB  0.05    *blue     violet                              C.I. No. 52010                                                                             3:1                                                              (Eastman Kodak)                                                                            formamide  0.05    dark blue dark blue                                        lauryl     0.05    *blue     violet                                           alcohol                                              129 thiazine                                                                              Methylene Violet                                                                           OBNB/OCNB  0.05    dark violet                                                                             dark violet                         C.I. No. 52041                                                                             3:1                                                              (Eastman Kodak)                                                   130 amino-  Murexide     OBNB/OCNB  0.2     *brown    yellow                      ketone  C.I. No. 56085                                                                             3:1        0.05    brownish yellow                                                                         yellow                              (Merck)                 0.005   yellow    yellow                  131 anthra- Savinyl Green B                                                                            OBNB/OCNB  0.2     dark green                                                                              dark green                  quinone (Sandoz)     3:1        0.05    dark green                                                                              green                               C.I. Solvent green 19   0.005   green     light green                                      formamide  0.2     *dark green                                                                             dark green                                                  0.05    *dark green                                                                             green                                            lauryl     0.2     dk bluish green                                                                         green                                            alcohol    0.05    bluish green                                                                            green                                                       0.005   green     light green             132 anthra- Savinyl Blue RS                                                                            OBNB/OCNB  0.2     dark blue dark blue                           (Sandoz)     3:1        0.05    dark blue blue                                C.I. Solvent blue 45    0.005   blue      greenish blue                                    formamide  0.2     *dark blue                                                                              dark blue                                                   0.05    *blue     blue                                             lauryl     0.2     dark blue dark blue                                        alcohol    0.05    violet-blue                                                                             blue                                                        0.005   blue      light blue              133 anthra- D + C green 6                                                                              OBNB/OCNB  0.2     dark green                                                                              dark green                  quinone (American Cyanimid)                                                                        3:1        0.05    dark green                                                                              green                               C.I. Solvent green 3    0.005   green     green                               C.I. No. 61565                                                                             lauryl     0.2     dk greenish                                                                             blue                                             alcohol    0.05    greenish blue                                                                           lt greenish blue                                            0.005   greenish blue                                                                           lt greenish blue        134 anthra- Blue VIF Organol                                                                           OBNB/OCNB  0.2     dark blue dark blue                   quinone (Ugine Kuhlmann)                                                                           3:1        0.05    dark blue blue                                C.I. Solvent blue 63    0.005   bluish green                                                                            bluish green                        C.I. No. 61520                                                                             formamide  0.2     *dark blue                                                                              blue                                                        0.05    *blue     blue                                             lauryl     0.2     dark blue dark blue                                        alcohol    0.05    dark blue blue                                                        0.005   blue      light blue              135 anthra- Alizarin     OBNB/OCNB  0.2     dark yellow                                                                             dark orange                 quinone C.I. Mordant red 11                                                                        3:1        0.05    dark yellow                                                                             dark yellow                         C.I. No. 58000          0.005   yellow    yellow                              (Fluka)                                                                                    lauryl     0.2     *brownish orange                                                                        brownish orange                                  alcohol                                                                       naphthalene                                                                              0.05    yellow    light orange            136 anthra- Alizarin Cyanin 2R                                                                         OBNB/OCNB  0.2     dark red  dark brown                  quinone C.I. Mordant blue 50                                                                       3:1        0.05    dark red  brown                               C.I. No. 58550          0.005   reddish pink                                                                            yellow                              ( H & W)                                                                                   lauryl     0.2     dark red  dark brown                                       alcohol    0.05    dark red  brown                                                       0.005   purple    pink                                             naphthalene                                                                              0.05    dark red  dark red                137 anthra- Celliton Blue Extra                                                                        OBNB/OCNB  0.2     dark blue dark green                  quinone C.I. Solvent blue 18                                                                       3:1        0.05    dark blue green                               Disperse blue 1         0.005   light green                                                                             light green                         C.I. No. 64500                                                                (BASF)       lauryl     0.2     dark blue blue                                             alcohol    0.05    vivid blue                                                                              light blue                                                  0.005   light blue                                                                              light blue                                       naphthalene                                                                              0.05    *dark blue                                                                              light blue              138 anthra- Alizarin Blue S                                                                            OBNB/OCNB  0.2     deep dark red                                                                           black                       quinone C.I. Mordant blue 27                                                                       3:1        0.05    dark red  greyish green                       C.I. No. 67415          0.005   dark orange                                                                             light green                         (H & W)                                                                                    lauryl     0.2     dk purple red                                                                           dark grey                                        alcohol    0.05    red purple                                                                              light purple                                                0.005   light blue                                                                              colorless                                        naphthalene                                                                              0.05    *dark red grey                    139 anthra- Nitrofast Green GSB                                                                        OBNB/OCNB  0.2     dark green                                                                              dark green                  quninone                                                                              C.I. Solvent green 3                                                                       3:1        0.05    dark green                                                                              dark green                          C.I. No. 61565          0.005   greenish blue                                                                           light green                         (Sandoz)                                                                                   lauryl     0.2     deep dark blue                                                                          deep dark blue                                   alcohol    0.05    dark blue blue                                                        0.005   blue      light blue              140 anthra- Alizarin Red S                                                                             OBNB/OCNB  0.2     dark orange                                                                             yellowish orange            quinone C.I. Mordant red 3                                                                         3:1        0.05    dark yellow                                                                             dark yellow                         C.I. No. 58005          0.005   yellow    yellow                              (Baker)                                                                                    lauryl     0.2     dk orange-yellow                                                                        dark yellow                                      alcohol    0.05    yellow    light yellow            141 anthra- quinolizarium                                                                              OBNB/OCNB  0.2     red       red                         quinone C.I. Mordant violet 26                                                                     3:1        0.05    orange-red                                                                              reddish orange                      C.I. No. 58500          0.005   reddish orange                                                                          dark yellow                         (Fluka)                                                                                    lauryl     0.2     *vermillion                                                                             red                                              alcohol    0.05    reddish orange                                                                          reddish pink                                                0.005   pinkish orange                                                                          pink                    142 anthra- Oil Blue N   OBNB/OCNB  0.2     deep blue deep green                  quinone C.I. Solvent blue 14                                                                       3:1        0.05    deep blue moss green                          C.I. No. 61555          0.005   greenish blue                                                                           bluish green                        (ICN-K&K)                                                         143 anthra- Soluary Purple                                                                             OBNB/OCNB  0.2     deep blue deep blue                   quinone C.I. Acid violet 431                                                                       3:1        0.05    deep blue bluish green                        C.I. No. 60730          0.05    light green                                                                             light green                         (ICN-K&K)                                                         144 anthra- Purpin       OBNB/OCNB  0.2     *orange   orange-red                  quinone C.I. No. 58205                                                                             3:1        0.05    orange    reddish orange                      (H & W)                                                                                    formamide  0.2     *dark red dark red                                                    0.05    dark red  dark red                                                    0.005   red       red                                              lauryl     0.2     *orange   orange                                           alcohol    0.05    orange    light orange                                                0.005   light orange                                                                            light orange            145 indigo  Indigo Synthetic                                                                           OBNB/OCNB  0.05    *dark blue                                                                              grey blue                           C.I. Vat blue 1                                                                            3:1                                                              (Fluka)                                                                                    lauryl     0.05    *blue     light blue                                       alcohol                                              146 indigo  Cromophtal Bordeaux                                                                        OBNB/OCNB  0.2     brown     reddish brown                       RS (Ciba-Geigy)                                                                            3:1        0.05    beige     beige-yellow                        C.I. Pigment red 88     0.005   yellow    yellow                              C.I. No. 73312                                                    147 indigo  Thioindigo Red                                                                             OBNB/OCNB  0.2     dk purple-red                                                                           dark purple                         C.I. Vat red 41                                                                            3:1        0.05    carmine   beige                               C.I. No. 73300          0.005   yellowish orange                                                                        yellow                              (ICN-K&K)                                                                                  lauryl     0.2     *dark red dark purple                                      alcohol    0.05    purple    light purple                                                0.005   light violet                                                                            light violet            148 indigo  Ciba Blue    OBNB/OCNB  0.2     deep blue green                               C.I. Vat blue 5                                                                            3:1        0.05    bluish green                                                                            light green                         C.I. No.73065           0.005   green     greenish yellow                     (ICN-K&L)                                                         149 indigo  Indigo Carmine                                                                             OBNB/OCNB  0.05    *yellowish green                                                                        yellowish green                     C.I. Acid hue 74                                                                           3:1                                                              C.I. No. 73015                                                                (Baker)                                                           150 phthalo-                                                                              Savinyl Blue GLS                                                                           OBNB/OCNB  0.05    bluish green                                                                            greenish blue               cyanine (Sandoz)     3:1                                                              C.I. Solvent blue 44                                              151 phthalo-                                                                              Irgalith Blue GLSM                                                                         OBNB/OCNB  0.05    greenish blue                                                                           blue                                (Ciba-Geigy) 3:1                                                              C.I. Pigment blue 15:3                                                        C.I. No.74160                                                     152 phthalo-                                                                              Phthalocyanine                                                                             OBNB/OCNB  0.05    dark green                                                                              dark grey green             cyanine C.I. Pigment blue 15                                                                       3:1                                                              C.I. No. 74160                                                    153 natural Alcannin     OBNB/OCNB  0.2     red       dark red                            C.I. Natural red 20                                                                        3:1        0.05    red       purple-red                          C.I. No. 75530          0.005   red       beige                               (H & W)                                                                                    lauryl     0.2     brownish red                                                                            light pink                                       alcohol                                              154 natural Curcumin     OBNB/OCNB  0.2     dark yellow                                                                             dark yellow                         C.I. Natural yellow 3                                                                      3:1        0.05    yellow    yellow                              C.I. No.75300           0.005   yellow    yellow                              (Merck)                                                           155 natural Quercitrindihydrate                                                                        OBNB/OCNB  0.2     yellow    yellow                              C.I. Natural yellow 10                                                                     3:1        0.05    yellow    yellow                              C.I. No. 75720          0.005   yellow    yellow                              (Carl Roth)                                                       156 inorganic                                                                             Prussian blue                                                                              OBNB/OCNB  0.2     *green    green                       pigments                                                                              C.I. Pigment blue 27                                                                       3:1        0.05    light green                                                                             light green                         C.I. No. 77510          0.005   yellowish green                                                                         yellowish green                     (M.C. & B.)                                                       157 monoazo Ceres Orange R                                                                             OBNB/OCNB  0.2     red orange                                                                              dark orange                         C.I. No. 12055                                                                             3:1        0.05    orange    orange                              C.I. Solvent yellow 14  0.005   orange    yellowish orange        158 monazo  Ceres Yellow 3G                                                                            OBNB/OCNB  0.2     orange    yellowish orange                    C.I. Solvent yellow 16                                                                     3:1        0.05    yellowish orange                                                                        yellow                              C.I. No. 12700          0.005   yellow    yellow                  159 monazo  4-phenylazo-1-naphtyl-                                                                     OBNB/OCNB  0.2     dk reddish brown                                                                        dark brown                          amine        3:1        0.05    reddish brown                                                                           brown                                                       0.005   brownish orange                                                                         yellow                  160 monazo  4-(4-Dimethylamino-                                                                        OBNB/OCNB  0.2     green     green                               1-naphtylazo)-3-                                                                           3:1        0.05    green     light green                         methoxybenzene          0.005   yellow    yellow                              sulfonic acid                                                     161 monoazo p-(p-Dimethylamino-                                                                        OBNB/OCNB  0.2     reddish orange                                                                          orange                              phenylazo)benzoic acid                                                                     3:1        0.05    orage     light orange                        sodium salt             0.005   light orange                                                                            yellow                  162 disazo  Ceres Red B  OBNB/OCNB  0.2     dark red  dark red                            C.I. No.26110                                                                              3:1        0.05    red       red                                 C.I. Solvent red 25     0.005   red       pinkish red             163 indamine                                                                              Binderscheler's Green                                                                      OBNB/OCNB  0.2     orange brown                                                                            beige                               C.I. No. 49405                                                                             3:1        0.05    orange brown                                                                            light beige                                                 0.005   yellow    yellow                  164         Phenylene Blue                                                                             OBNB/OCNB  0.2     dark blue bluish green                        (ICN-K&K)    3:1        0.05    dark blue light green                         Cat. No. 17371          0.005   greenish blue                                                                           yellowish green         165 azine   Amethyst Violet                                                                            OBNB/OCNB  0.2     purple    violet                              C.I. No.50225                                                                              3:1        0.05    purple red                                                                              violet                                                      0.005   purple red                                                                              pink                    166 anthraquinone                                                                         Alizarin Viridin                                                                           OBNB/OCNB  0.2     *green    green                               C.I. Acid green 41                                                                         3:1        0.05    light green                                                                             light green                         C.I. No. 62560          0.005   yellow    yellow                  167 unknown Ceres Blue R OBNB/OCNB  0.2     deep blue blue                                C.I. Solvent blue 78                                                                       3:1        0.05    blue      light blue                                                  0.005   greenish blue                                                                           bluish                  __________________________________________________________________________                                                          green                    *not completely dissolved.                                                    *.sup.2 after one week storage at room temperature nearly colorless.     

EXAMPLE 11

This example gives combinations tested for color change in varioussolvents and at different combinations. These combinations include:

(a) mixtures of Group III moieties;

(b) mixtures of acids having a pK less than about four and basic dyes orbasic indicators;

(c) mixtures of organic acids having a pK less than about two and acidicdyes or acidic indicators;

(d) mixtures of Group III moieties and organic acidic compounds with apK less than about 4;

(e) mixtures of Group III moieties and basic dyes or basic indicators;and

(f) mixtures of a dye having a molecular structure containing a lactonedye and acids.

The results are given in Table 3.

                                      TABLE 3                                     __________________________________________________________________________                     Total                                                                         Concentration   Color                                        No.                                                                              Organic Compounds                                                                           % m/m   Solvent Liquid  Solid                                __________________________________________________________________________    1  Quinaldine red/                                                                             0.05    OCNB    wine red                                                                              orange brown                            acridine orange 1:1                                                        2  Toluidine blue 0/                                                                           0.05    OCNB    green   brown                                   acridine orange 1:1                                                        3  Same mixture  0.05    OCNB/OBNB                                                                             green   brownish yellow                                               1:3                                                  4  Same mixture  0.05    t. but- green   brownish yellow                                               anol                                                 5  Same mixture  0.05    sym.    green   brown                                                         trioxane*                                            6  Acridine orange/                                                                            0.015   OCNB    red     reddish-orange                          fuchsin 2:1                                                                7  Bromophenol blue/                                                                           0.05    OCNB/OBNB                                                                             blue    greenish yellow                         pinacyanol iodide     1:3                                                  8  Chlorophenol red/                                                                           0.05    OCNB/OBNB                                                                             greenish blue                                                                         light yellowish                         pinacyanol iodide     1:3             brown                                9  Chlorophenol blue/                                                                          0.05    OCNB/OBNB                                                                             blue    green                                   pinacyanol iodide     1:3                                                  10 Chlorocresol green/                                                                         0.05    OCNB/OBNB                                                                             blue    moss green                              pinacyanol iodide     1:3                                                  __________________________________________________________________________     *timer of formaldehyde.                                                      11 Phthalocyanine/                                                                             0.05    OCNB/OBNB                                                                             blue    brown                                   pinacyanol iodide     1:3                                                  12 Bromochlorophenol blue/                                                                     0.05    OCNB/OBNB                                                                             greenish blue                                                                         yellowish brown                         pinacyanol chloride 5:1                                                                             1:3                                                  13 Bromocresol purple/                                                                         0.05    OCNB/OBNB                                                                             red orange                                                                            orange                                  2-(p-dimethylaminostyryl)-                                                                          1:3                                                     1-ethyl-pyridinium iodide                                                  14 Bromochlorophenol blue/                                                                     0.05    OCNB/OBNB                                                                             red orange                                                                            yellow                                  2-(p-dimethylaminostyryl)-                                                                          1:3                                                     1-ethyl-pyridinium iodide                                                  15 Bromophenol red/                                                                            0.05    OCNB/OBNB                                                                             red orange                                                                            orange                                  2-(p-dimethylaminostyryl)-                                                                          1:3                                                     1-ethylpyridinium iodide                                                   16 Chlorocresol green/                                                                         0.05    OCNB/OBNB                                                                             red orange                                                                            yellow                                  2-(p-dimethylaminostyryl)-                                                                          1:1                                                     1-ethyl-pyridinium iodide                                                  17 Bromophenol blue/                                                                           0.05    OCNB/OBNB                                                                             blue    green                                   crystal violet        1:3                                                  18 Chlorophenol red/                                                                           0.05    OCNB/OBNB                                                                             green   red                                     cryptocyanine                                                              19 Bromochlorophenol blue/                                                                     0.05    OCNB/OBNB                                                                             green   yellow                                  cryptocyanine         1:3                                                  20 Chlorophenol red/                                                                           0.05    OCNB/OBNB                                                                             green   red                                     Dicyanine A           1:3                                                  21 Bromochlorophenol blue/                                                                     0.05    OCNB/OBNB                                                                             green   yellow                                  Dicyanine A           1:3                                                  22 Cromocresol purple/                                                                         0.05    OCNB/OBNB                                                                             greenish blue                                                                         green                                   3,3'-diethylthiadicarbo-                                                                            1:3                                                     cyanine iodide                                                             23 Bromophenol blue/                                                                           0.05    OCNB/OBNB                                                                             greenish blue                                                                         yellow green                            3,3'-diethylthiadicarbo-                                                                            1:3                                                     cyanine iodide                                                             24 Bromochlorophenol blue/                                                                     0.05    OCNB/OBNB                                                                             red     yellow orange                           1,1'-diethyl-2,2'-    1:3                                                     cyanine iodide                                                             25 Chlorophenol red/                                                                           0.05    OCNB/OBNB                                                                             green   red                                     phthalocyanine        1:3                                                  26 Bromophenol blue/                                                                           0.05    OCNB/OBNB                                                                             red     yellow                                  ethyl red             1:3                                                  27 Chlorophenol blue/                                                                          0.05    OCNB/OBNB                                                                             red     yellow                                  ethyl red             1:3                                                  28 Chlorophenol red/                                                                           0.05    OCNB/OBNB                                                                             red     orange                                  ethyl red 3:1         1:3                                                  29 Bromocresol purple/                                                                         0.05    OCNB/OBNB                                                                             red     yellow                                  ethyl red             1:3                                                  30 Bromochlorophenol blue/                                                                     0.05    OCNB/OBNB                                                                             purple red                                                                            yellow                                  ethyl red             1:3                                                  31 Bromophenol red/                                                                            0.05    OCNB/OBNB                                                                             reddish violet                                                                        violet                                  ethyl red 3:1         1:3                                                  32 Bromochlorophenol blue/                                                                     0.05    OCNB/OBNB                                                                             dark blue                                                                             yellow                                  ethyl red/pinacyanol iodide                                                                         1:3                                                  33 Murexide/quinaldine red                                                                     0.05    OCNB/OBNB                                                                             purple  light brownish                                                1:3     yellow                                       34 Bromochlorophenol blue/                                                                     0.05    OCNB/OBNB                                                                             purple  yellow                                  Quinaldine red/pinacyanol                                                                           1:3                                                     iodide                                                                     35 Phthalocyanine/                                                                             0.05    OCNB/OBNB                                                                             violet  dark brown                              quinaldine red        1:3                                                  36 Fluorescein/pinacyanol                                                                      0.05    OCNB/OBNB                                                                             blue    brownish purple                         iodide                1:3                                                  37 Trichloroacetic acid/                                                                       0.05    OCNB/OBNB                                                                             green   yellow                                  cryptocyanine         1:3                                                  38 Maleic acid*/cryto-                                                                         0.05    OCNB/OBNB                                                                             green   light yellow                            cyanine               1:3             green                                39 Maleic acid/dicyanine A                                                                     0.05    OCNB/OBNB                                                                             green   light yellow                                                  1:3             green                                40 Naphthalenesulphonic                                                                        0.05    OCNB/OBNB                                                                             greenish yellow                                                                       yellow                                  acid/dicyanine A      1:3                                                  41 Trichloroacetic acid/                                                                       0.05    OCNB/OBNB                                                                             greenish yellow                                                                       yellow                                  dicyanine A           1:3                                                  42 3,4,5,6-tetrabromophenol-                                                                   0.05    OCNB/OBNB                                                                             red orange                                                                            orange                                  sulphonephthalein/2-  1:3                                                     (p-dimethylaminostyryl)-                                                      1-ethyl-pyridinium iodide                                                  43 Thymolphthalein/ethyl red                                                                   0.05    OCNB/OBNB                                                                             red     purple                                                        1:3                                                  44 3,4,5,6-tetrabromophenol-                                                                   0.05    OCNB/OBNB                                                                             red     brownish red                            sulphonephthalein/ethyl red                                                                         1:3                                                  __________________________________________________________________________     *maleic acid is poor soluble in the solvent.                                 45 Naphthalenesulphonic                                                                        0.05    OCNB/OBNB                                                                             red     yellow                                  acid/ethyl red        1:3                                                  46 2,4-dinitrobenzene-                                                                         0.30    OCNB    red     yellow                                  sulphonic acid/ethyl red 5:1                                               47 Naphthalenesulphonic acid/                                                                  0.05    OCNB/OBNB                                                                             purple red                                                                            yellow                                  quinaldine red        1:3                                                  48 Trichloroacetic acid/                                                                       0.05    OCNB/OBNB                                                                             purple  yellow                                  quinaldine red        1:3                                                  49 2,4-dinitrobenzene-                                                                         0.30    OCNB    red     yellow                                  sulphonic acid/                                                               quinaldine red 5:1                                                         50 3,4,5,6-tetrabromophenol-                                                                   0.05    OCNB/OBNB                                                                             reddish pink                                                                          yellow                                  sulphonephthalein/    1:3                                                     quinaldine red                                                             51 Naphthalenesulphonic acid/                                                                  0.05    OCNB/OBNB                                                                             red     yellow                                  1,1'-diethyl-2,2'-cyanine                                                     iodide                                                                     52 Trichloroacetic acid/1,1'-                                                                  0.05    OCNB/OBNB                                                                             red     yellow                                  diethyl-2,2'-cyanine iodide                                                                         1:3                                                  53 Maleic acid*/1,1'-di-                                                                       0.05    OCNB/OBNB                                                                             red     yellow                                  ethyl-2,2'cyanine iodide                                                                            1:3                                                  54 Trichloroacetic acid/3,3'-                                                                  0.05    OCNB/OBNB                                                                             blue green                                                                            light rose                              diethylthiadicarbocyanine                                                                           1:3                                                     iodide                                                                     55 Naphthalenesulphonic                                                                        0.05    OCNB/OBNB                                                                             green   yellow brown                            acid/crystal violet   1:3                                                  56 Maleic acid*/crystal                                                                        0.05    OCNB/OBNB                                                                             blue    green                                   violet                1:3                                                  57 Dichloroacetic acid/                                                                        0.05    OCNB/OBNB                                                                             blue    green                                   crystal violet 1:1    1:3                                                  58 Dichloroacetic acid/                                                                        0.20    OCNB/OBNB                                                                             blue    dark green                              crystal violet 3:1    1:3                                                  59 Naphthalenesulphonic                                                                        0.05    OCNB/OBNB                                                                             green   yellow                                  acid/ethyl violet     1:3                                                  60 Trichloroacetic acid/                                                                       0.05    OCNB/OBNB                                                                             green   yellow                                  ethyl violet          1:3                                                  61 Maleic acid*/ethyl                                                                          0.05    OCNB/OBNB                                                                             blue    yellowish green                         violet                1:3                                                  62 Naphthalenesulphonic                                                                        0.05    OCNB/OBNB                                                                             purple  yellow                                  acid/basic fuchsin    1:3                                                  63 Naphthalenesulphonic                                                                        0.05    OCNB    purple  greenish                                acid/basic fuchsin 4:1                                                     64 Maleic acid*/basic fuchsin                                                                  0.05    OCNB/OBNB                                                                             red     blue violet                                                   1:3                                                  65 Chloroanilic acid/                                                                          0.05    OCNB/OBNB                                                                             red     grey                                    basic fuchsin         1:3                                                  66 Bromophenol blue/                                                                           0.05    OCNB/OBNB                                                                             red     moss green                              basic fuchsin         1:3                                                  67 Bromophenol red/                                                                            0.05    OCNB/OBNB                                                                             green   dark green                              brilliant green       1:3                                                  68 Bromochlorophenol blue/                                                                     0.05    OCNB/OBNB                                                                             blue    green                                   brilliant green       1;3                                                  69 bromochlorophenol blue/                                                                     0.05    OCNB/OBNB                                                                             blue    light moss                              ethyl violet          1:3                                                  70 Cryptocyanine/5-(p-dimethyl                                                                 0.05    OCBN/OBNB                                                                             dark yellow                                                                           dark brown                              aminobenzilidene)rhodanine                                                                          1:3                                                  __________________________________________________________________________     *maleic acid is poor soluble in the solvents.                                71 Dicyanin A/5-(p-dimethyl-                                                                     0.05    OCNB/OBNB                                                                             green   purple                                aminobenzilidene)rhodanine                                                                            1:3                                                72 Sodium phthalocyanine/                                                                        0.05    OCNB/OBNB                                                                             blue    brown                                 pinacyanol iodide       1:3                                                73 Sodium phthalocyanine/                                                                        0.05    OCNB/OBNB                                                                             violet  light brown                           quinaldine red          1:3                                                74 Sodium phthalocyanine/                                                                        0.05    OCNB/OBNB                                                                             green   red                                   chlorophenol red        1:3                                                75 Naphthalenesulphonic acid/                                                                    0.05    OCNB/OBNB                                                                             yellow  very light red                        bromochlorophenol blue  1:3                                                76 Naphthalenesulphonic acid/                                                                    0.05    OCNB/OBNB                                                                             orange  red                                   chlorophenol blue       1:3                                                77 Naphthalesulphonic acid/                                                                      0.05    OCNB/OBNB                                                                             orange  red                                   bromocresol purple      1:3                                                78 Crystal violet lactone/                                                                       0.10    OCNB/OBNB                                                                             yellow  blue                                  phenol 1:1              1:3                                                79 Crystal violet lactone/                                                                       0.05    OCNB/OBNB                                                                             yellowish green                                                                       blue                                  bisphenol A 1:1         1:3                                                80 Crystal violet lactone/                                                                       0.05    OCNB/OBNB                                                                             green   green                                 benzoic acid 1:1        1:3                                                81 Crystal violet lactone/                                                                       0.05    OCNB/OBNB                                                                             yellowish green                                                                       greenish blue                         3-nitrophenol 1:1       1:3                                                82 Crystal violet lactone/                                                                       0.05    OCNB/OBNB                                                                             yellowish green                                                                       blue                                  pyrocatechol 1:1        1:3                                                __________________________________________________________________________     ratios are mass ratios.                                                  

EXAMPLE 12

The following Table lists compounds found to be unsatisfactory as GroupIII moieties:

                                      TABLE 4                                     __________________________________________________________________________                                Concentration                                                                         Color                                     Class   Dye         Solvent % (m/m) Liquid   Solid                            __________________________________________________________________________    nitroso 2 Nitroso-1-Naphtol                                                                       OBNB/OCNB                                                                             0.2     brown    brown                                    Mordant dye 3:1     0.05    yellowish brown                                                                        yellowish brown                          C.I. No. 10010      0.005   yellow   yellow                                   (Fluka)                                                               nitro   Salicyl Yellow A and B                                                                    OBNB/OCNB                                                                             0.2     *yellowish brown                                                                       yellowish brown                          Acid dye    3:1                                                               C.I. No. 10300                                                                (Merck)                                                               monoazo Orasol Red G                                                                              OBNB/OCNB                                                                             0.05    red      red                                      C.I. Solvent red 125                                                                      3:1                                                               (Ciba-Geigy)                                                          monoazo Orasol Red B                                                                              OBNB/OCNB                                                                             0.05    dark red dark red                                 C.I. Solvent red F                                                                        3:1                                                               (Ciba-Geigy)                                                          monoazo Tropeolin O OBNB/OCNB                                                                             0.2     dark yellow                                                                            dark yellow                              C.I. Acid orange 6                                                                        3:1     0.05    dark yellow                                                                            dark yellow                              Food Yellow 8       0.005   yellow   yellow                                   C.I. No. 14270                                                                (Baker)                                                               monoazo Sudan red G OBNB/OCNB                                                                             0.2     red      red                                      C.I. Solvent Red 1                                                                        3:1     0.05    dark orange                                                                            dark orange                              C.I. No. 12150      0.005   orange   orange                                   (BASF)                                                                        Orange G    OBNB/OCNB                                                                             0.2     orange   orange                                   C.I. Acid orange 10                                                                       3:1     0.05    dark yellow                                                                            dark yellow                              Food orange 4       0.005   yellow   yellow                                   C.I. No. 16230                                                                (Fluka)                                                               monoazo Alizaren yellow G.G.                                                                      OBNB/OCNB                                                                             0.2     *dark yellow                                                                           dark yellow                              C.I. Mordant yellow 1                                                                     3:1                                                               C.I. No. 14025                                                                (Merck)                                                               monoazo Calcon      OBNB/OCNB                                                                             0.2     *greenish brown                                                                        greenish brown                           C.I. Mordant black 17                                                                     3:1                                                               C.I. No. 15705                                                                (Merck)                                                               monoazo Awaranth    OBNB/OCNB                                                                             0.2     *brownish green                                                                        brownish green                           C.I. Acid red 27                                                                          3:1                                                               Food red G                                                                    C.I. No. 16185                                                                (Merck)                                                               monoazo Tartiazine  OBNB/OCNB                                                                             0.2     orange   orange                                   C.I. Pigment yellow 100                                                                   3:1     0.05    dark yellow                                                                            dark yellow                              C.I. No. 19140:1    0.005   yellow   yellow                                   (I.G. Farber)                                                         monoazo Orange I    OBNB/OCNB                                                                             0.2     brown    brown                                    C.I. Acid orange 20                                                                       3:1     0.05    brownish yellow                                                                        brownish yellow                          C.I. No. 14600      0.005   yellow   yellow                                   (Fluka)                                                               monoazo Eriochrome blue Blk B                                                                     OBNB/OCNB                                                                             0.2     black    black                                    C.I. Mordant Black 3                                                                      3:1     0.05    greenish brown                                                                         greenish brown                           C.I. No. 14640      0.005   yellow   yellow                                   (Fluka)                                                               monoazo Thiazin Red R                                                                             OBNB/OCNB                                                                             0.2     green    green                                    C.I. Direct red 45                                                                        3:1     0.05    greenish yellow                                                                        greenish yellow                          Food red 13         0.005   yellow   yellow                                   C.I. No. 14780                                                                (Fluka)                                                               monoazo Orange GGN  OBNB/OCNB                                                                             0.2     red orange                                                                             red orange                               C.I. Food orange 2                                                                        3:1     0.05    orange   orange                                   C.I. No. 15980      0.005   yellow   yellow                                   (Merck)                                                               monoazo Chromotrope 2B                                                                            OBNB/OCNB                                                                             0.2     *green   green                                    C.I. Acid red 176                                                                         3:1                                                               Mordant black 93                                                              C.I. No. 16575                                                                (Fluka)                                                               monoazo Eriochrome Blue SE                                                                        OBNB/OCNB                                                                             0.2     *light green                                                                           light green                              C.I. Mordant blue 133:1                                                       C.I. No. 16680                                                                (ICN-K & K)                                                           monoazo Eriochrome Red B                                                                          OBNB/OCNB                                                                             0.2     *reddish brown                                                                         reddish brown                            C.I. Mordant red 7                                                                        3:1                                                               C.I. No. 18760                                                                (Fluka)                                                               monoazo Sudans      OBNB/OCNB                                                                             0.2     *green   green                                    C.I. Acid red 60                                                                          3:1                                                               Mordant blue 81                                                               C.I. No. 16645                                                                (Fluka)                                                               monoazo Methanil Yellow                                                                           OBNB/OCNB                                                                             0.2     dark yellow                                                                            dark yellow                              C.I. Acid dye                                                                             3:1     0.05    yellow   yellow                                   C.I. No. 15165      0.005   yellow   yellow                                   (Baker)                                                               monoazo Orange II   OBNB/OCNB                                                                             0.2     *red orange                                                                            red orange                               C.I. Acid orange 7                                                                        3:1                                                               C.I. No. 15510                                                                (Fluka)                                                               monoazo Aniline Yellow                                                                            OBNB/OCNB                                                                             0.2     orange   orange                                   C.I. Solvent yellow 1                                                                     3:1     0.05    dark yellow                                                                            dark yellow                              C.I. No. 11000      0.005   yellow   yellow                                   (MC & B)                                                              monoazo Ponceau 3R  OBNB/OCNB                                                                             0.2     *brownish red                                                                          brownish red                             Acid dye    3:1                                                               C.I. No. 16155                                                                (MC & B)                                                              disazo  Organol Yellow JR                                                                         OBNB/OCNB                                                                             0.05    orange   orange                                   (Ugine Kuhlmann)                                                                          3:1                                                       disazo  Congo Red   OBNB/OCNB                                                                             0.2     *red     red                                      C.I. No. 22110                                                                            3:1                                                               Direct dye                                                                    (Baker)                                                               disazo  Sudan Red 7B                                                                              OBNB/OCNB                                                                             0.2     dark red dark red                                 C.I. Solvent red 1G                                                                       3:1     0.05    red      red                                      C.I. No. 26050      0.005   light red                                                                              light red                                (Edward Gurr)                                                         disazo  Oil red 0   OBNB/OCNB                                                                             0.2     very dark red                                                                          very dark red                            C.I. Solvent red 27                                                                       3:1     0.05    dark red dark red                                 C.I. No. 26125      0.005   red      red                                      (Baker)                                                               disazo  Evans Blue  OBNB/OCNB                                                                             0.2     *green   green                                    C.I. Direct blue 533:1                                                        C.I. No. 23860                                                                (Merck)                                                               disazo  Naptal Blue Black B                                                                       OBNB/OCNB                                                                             0.2     *green   green                                    C.I. Acid black 1                                                                         3:1                                                               C.I. No. 20470                                                                (Fluka)                                                               disazo  Bismarck Brown R                                                                          OBNB/OCNB                                                                             0.2     very dark green                                                                        very dark green                          C.I. Basic brown 4                                                                        3:1     0.05    green    green                                    C.I. No. 21000      0.005   light green                                                                            light green                              (Fluka)                                                               disazo  Ponceau BS  OBNB/OCNB                                                                             0.2     *brownish red                                                                          brownish red                             C.I. acid red 66                                                                          3:1                                                               C.I. No. 26905                                                                (Fluka)                                                               disazo  Ponceau S   OBNB/OCNB                                                                             0.2     *brownish yellow                                                                       brownish yellow                          C.I. Acid red 112                                                                         3:1                                                               C.I. No. 27195                                                                (Fluka)                                                               disazo  Benzopurpurin 4B                                                                          OBNB/OCNB                                                                             0.2     *brown   brown                                    C.I. Direct red 2                                                             C.I. No. 23500                                                                (MC & B)                                                              disazo  Sudan III   OBNB/OCNB                                                                             0.2     very dark red                                                                          very dark red                            C.I. Solvent red 23                                                                       3:1     0.05    dark red dark red                                 C.I. No. 26100      0.005   red      red                                      (Baker)                                                               disazo  Crocein Scarlet 1700, 3B                                                                  OBNB/OCNB                                                                             0.2     brownish red                                                                           brownish red                             C.I. Acid red 73                                                                          3:1                                                               C.I. No. 27290                                                                (MC & B)                                                              trisazo Direct Yellow 62                                                                          OBNB/OCNB                                                                             0.2     yellow   yellow                                   C.I. No. 36900                                                                            3:1     0.05    yellow   yellow                                   (MC & B)            0.005   yellow   yellow                           polyazo Solophenyl Red 3BL                                                                        OBNB/OCNB                                                                             0.05    non soluble                                       Direct red 80                                                                             3:1                                                               (Ciba-Geigy)                                                          azoic   Fast Violet Salt                                                                          OBNB/OCNB                                                                             0.2     yellow   yellow                                   C.I. No. 37165                                                                            3:1     0.05    yellow   yellow                                   (Fluka)             0.005   yellow   yellow                           azoic   Fast Red Salt RC                                                                          OBNB/OCNB                                                                             0.2     yellow   yellow                                   C.I. No. 37120                                                                            3:1     0.05    yellow   yellow                                   (Fluka)             0.005   yellow   yellow                           azoic   Fast Red Salt B                                                                           OBNB/OCNB                                                                             0.2     yellow   yellow                                   C.I. No. 37125                                                                            3:1     0.05    yellow   yellow                                   (Fluka)             0.005   yellow   yellow                           triaryl Methyl Green                                                                              OBNB/OCNB                                                                             0.2     dark green                                                                             dark green                       methane C.I. Basic blue 20                                                                        3:1     0.05    green    green                                    C.I. No. 42505      0.005   light green                                                                            light green                              (Merck)                                                               triaryl Water Blue Standard                                                                       OBNB/OCNB                                                                             0.2     *green   green                            methane (Fluka)     3:1     0.05                                                      C.I. solvent blue 3 0.005                                                     C.I. No. 42775                                                        triaryl Acid Fuchsin                                                                              OBNB/OCNB                                                                             0.2     dark green                                                                             dark green                       methane C.I. Acid violet 1g                                                                       3:1     0.05    light green                                                                            light green                              C.I. No. 42685      0.005   yellow   yellow                                   (Fluka)                                                               triaryl Alkaline Blue 6B                                                                          OBNB/OCNB                                                                             0.2     dark green                                                                             dark green                       methane C.I. Acid blue 119                                                                        3:1     0.05    green    green                                    C.I. No. 42765      0.005   light green                                                                            light green                              (Baker)                                                               triaryl Patent Blue V                                                                             OBNB/OCNB                                                                             0.2     blue     blue                             methane C.I. Acid blue 3                                                                          3:1     0.05    blue     blue                                     Food blue 5         0.005   green    green                                    C.I. No. 42051                                                                (Merck)                                                               triaryl Water blue  OBNB/OCNB                                                                             0.2     *green   green                            methane C.I. Acid blue 22                                                             C.I. No. 42755                                                                (Fluka)                                                               triaryl Aurine      OBNB/OCNB                                                                             0.2     dark orange                                                                            dark orange                      methane C.I. No. 43800                                                                            3:1                                                               (H & W)                                                               triaryl Eriochrome Cyamin R                                                                       OBNB/OCNB                                                                             0.2     brown    brown                            methane C.I. Mordant blue 3                                                                       3:1     0.05    dark yellow                                                                            dark yellow                              C.I. No. 43820      0.005   yellow   yellow                                   (Merck)                                                               triaryl Eriochromaznol B                                                                          OBNB/OCNB                                                                             0.2     brown    brown                            methane C.I. Mordant blue 1                                                                       3:1     0.05    brownish yellow                                                                        brownish yellow                          C.I. No. 43830      0.005   yellow   yellow                                   (Ciba-Geigy)                                                          triaryl Fast Green FCF                                                                            OBNB/OCNB                                                                             0.2     *moss green                                                                            moss green                       methane C.I. Food green 3                                                                         3:1     0.05    light green                                                                            light green                              C.I. No. 42053      0.005   greenish yellow                                                                        greenish yellow                          (MC & B)                                                              triaryl Methyl Violet Base                                                                        OBNB/OCNB                                                                             0.2     very dark blue                                                                         very dark blue                   methane C.I. Solvent violet 8                                                                     3:1     0.05    very dark blue                                                                         very dark blue                           C.I. No. 42535:1    0.005   dark blue                                                                              dark blue                                (MC & B)                                                              triaryl Naphtalene Green V                                                                        OBNB/OCNB                                                                             0.2     very dark green                                                                        very dark green                  methane C.I. Acid green 16                                                                        3:1     0.05    dark green                                                                             dark green                               C.I. No. 44025      0.005   green    green                                    (MC & B)                                                              triaryl Light Green SF                                                                            OBNB/OCNB                                                         yellowish   3:1     0.2     green    green                                    C.I. Acid green 5   0.05    light green                                                                            light green                              C.I. Food green 2   0.005   very light green                                                                       very light green                         C.I. No. 42095                                                                (Fluka)                                                               triaryl Alkaline Blue                                                                             OBNB/OCNB                                                                             0.2     dark blue                                                                              dark blue                        methane C.I. Acid blue 110                                                                        3:1     0.05    bluish green                                                                           bluish green                             C.I. No. 42750      0.005   light green                                                                            light green                              (Merck)                                                               triaryl Chromarurol S                                                                             OBNB/OCNB                                                                             0.2     brown    brown                            methane C.I. Mordant blue 2g                                                                      3:1     0.05    brownish green                                                                         brownish green                           C.I. No. 43825      0.005   yellow   yellow                                   (Fluka)                                                               triaryl Victoria Blue B                                                                           OBNB/OCNB                                                                             0.2     dark blue                                                                              dark blue                        methane C.I. Basic blue 26                                                                        3:1     0.05    dark blue                                                                              dark blue                                C.I. No. 40445      0.005   dark blue                                                                              dark blue                                (Fluka)                                                               xanthene                                                                              Dichlorofluorescein                                                                       OBNB/OCNB                                                                             0.2     dark yellow                                                                            dark yellow                              C.I. Solvent orange 32                                                                    3:1     0.05    dark yellow                                                                            dark yellow                              C.I. No. 45365      0.005   yellow   yellow                                   (Fluka)                                                               xanthene                                                                              Acridine red                                                                              OBNB/OCNB                                                                             0.2     red      red                                      C.I. No. 45000                                                                            3:1     0.05    red      red                                      (MC & B)            0.005   red      red                              xanthene                                                                              Violamine 3B                                                                              OBNB/OCNB                                                                             0.2     *green   green                                    C.I. Acid blue 1g                                                                         3:1                                                               C.I. No. 45205                                                                (ICN-K & K)                                                           acidine Rivanol     OBNB/OCNB                                                                             0.2     yellow   yellow                                   (ICN-K & K) 3:1     0.05    yellow   yellow                                                       0.005   yellow   yellow                           acidine Proflavine  OBNB/OCNB                                                                             0.2     *yellow  yellow                                   (ICN-K & K) 3:1                                                       quinoline                                                                             Quinoline Yellow                                                                          OBNB/OCNB                                                                             0.2     yellow   yellow                                   C.I. Acid yellow 3                                                                        3:1     0.05    yellow   yellow                                   Food yellow 13      0.005   yellow   yellow                                   C.I. No. 47005                                                                (Fluka)                                                               azine   Indulin Water Soluble                                                                     OBNB/OCNB                                                                             0.2     *light green                                                                           light green                              C.I. Acid blue 20                                                                         3:1                                                               C.I. No. 50405                                                                (Fluka)                                                               azine   Neutral Violet                                                                            OBNB/OCNB                                                                             0.2     *green   green                                    C.I. No. 50030                                                                            3:1     0.05    light green                                                                            light green                              (ICN-K & K)         0.005   greenish yellow                                                                        greenish yellow                  azine   Magdala Red OBNB/OCNB                                                                             0.2     greenish greenish                                 C.I. Basic red 6                                                                          3:1     0.05    yellow   yellow                                   C.I. No. 50375      0.005   yellow   yellow                                   (ICN-K & K)                                                           azine   Indulin Alcohol                                                                           OBNB/OCNB                                                                             0.2     green    green                                    soluble     3:1                                                               C.I. Solvent Green  0.05    light green                                                                            light green                              C.I. No. 50400      0.005   greenish yellow                                                                        greenish yellow                          (ICN-K & K)                                                           oxazine Sandorin Violet Blue                                                                      OBNB/OCNB                                                                             0.2     dark violet                                                                            dark violet                              C.I. Pigment violet 23                                                                    3:1     0.05                                                      C.I. No. 51319                                                                (Sandoz)    lauryl alcohol                                                                        0.05    violet   violet                           oxazine Brilliant Cresyl Blue                                                                     OBNB/OCNB                                                                             0.2     dark blue                                                                              dark blue                                C.I. No. 51010                                                                            3:1     0.05    dark blue                                                                              dark blue                                (Merck)             0.005   green    green                            oxazine Capri Blue  OBNB/OCNB                                                                             0.2     dark blue                                                                              dark blue                                C.I. No. 51015                                                                            3:1     0.05    blue     blue                                     (ICN-K & K)         0.005   bluish green                                                                           bluish green                     oxazine Iris Blue   OBNB/OCNB                                                                             0.2     *greenish                                                                              greenish                                 C.I. No. 51400                                                                            3:1                                                               (ICN-K & K)                                                           anthraquinone                                                                         Chromophtal Blue A3R                                                                      OBNB/OCNB                                                                             0.2     dark blue                                                                              dark blue                                C.I. Vat blue 4                                                                           3:1     0.05    dark blue                                                                              dark blue                                Food blue 4         0.005   green    green                                    Pigment blue 60                                                               C.I. No. 69800                                                                (Ciba-Geigy)                                                          anthraquinone                                                                         Chromophtal Red A3B                                                                       OBNB/OCNB                                                                             0.2     dark red dark red                                 C.I. Pigment red 177                                                                      3:1     0.05    red      red                                      C.I. No. 65300      0.005   light red                                                                              light red                                (Ciba-Geigy)                                                          anthroquinone                                                                         Celliton fast Blue FFG                                                                    OBNB/OCNB                                                                             0.2     dark blue                                                                              dark blue                                C.I. Disperse blue 6                                                                      3:1     0.05    dark green                                                                             dark green                               C.I. No. 62050      0.005   light green                                                                            light green                              (BASF)                                                                anthroquinone                                                                         Anthra Purpurin                                                                           OBNB/OCNB                                                                             0.2     orange brown                                                                           orange brown                             C.I. Mordant dye                                                                          3:1     0.05    yellow   yellow                                   C.I. No. 58225      0.005   yellow   yellow                                   (H & W)                                                               anthroquinone                                                                         Anthracene Blue WR                                                                        OBNB/OCNB                                                                             0.2     *greenish yellow                                                                       greenish yellow                          C.I. Mordant blue 32                                                          C.I. No. 58605                                                                (H & W)                                                               anthroquinone                                                                         Anthraquinone Violet R                                                                    OBNB/OCNB                                                                             0.2     *moss green                                                                            moss green                               C.I. Acid violet 34                                                                       3:1                                                               C.I. No. 61710                                                                (MC & B)                                                              anthroquinone                                                                         Acid Alizarin Blue BB                                                                     OBNB/OCNB                                                                             0.2     *green   *green                                   C.I. Mordant blue 23                                                                      3:1                                                               C.I. No. 58610                                                                (ICN-K & K)                                                           anthroquinone                                                                         Alizarin Blue Black B                                                                     OBNB/OCNB                                                                             0.2     *moss green                                                                            moss green                               C.I. Mordant black 13                                                         C.I. No. 63615                                                                (MC & B)                                                              anthroquinone                                                                         Alizarin Brilliant                                                                        OBNB/OCNB                                                                             0.2     *green   green                                    Blue BS     3:1                                                               C.I. Acid blue 45                                                             C.I. No. 63010                                                                (ICN-K & K)                                                           phtalocamine                                                                          Orasol Blue OBNB/OCNB                                                                             0.05    greenish blue                                                                          greenish blue                            Brilliant GN                                                                              3:1                                                               C.I. Solvent blue 67                                                          (Ciba-Geigy)                                                          phtalocamine                                                                          Orasol Blue 2 GLN                                                                         OBNB/OCNB                                                                             0.05    bluish green                                                                           bluish green                             (Ciba-Geigy)                                                                              3:1                                                       phtalocamine                                                                          Solphenyl Turquois                                                                        OBNB/OCNB                                                                             0.05    *green   green                                    blue GRL    3:1                                                               C.I. direct blue 18g                                                          (Ciba-Geigy)                                                          phtalocamine                                                                          Sandorin Green GLS                                                                        OBNB/OCNB                                                                             0.05    green    green                                    C.I. Pigment green 7                                                                      3:1                                                               C.I. No. 74260                                                                (Sandoz)                                                                                  lauryl alcohol                                                                        0.05    light green                                                                            light green                      phtalocamine                                                                          Solar Turquois                                                                            OBNB/OCNB                                                                             0.05    *yellowish green                                                                       yellowish green                          blue GLL    3:1                                                               C.I. Direct blue 86                                                           C.I. No. 74180                                                                (Sandoz)                                                              natural Cochineal   OBNB/OCNB                                                                             0.2     *yellow  yellow                                   C.I. Natural red 4                                                                        3:1                                                               C.I. No. 75470                                                                (Kon. Pharm. Fab.)                                                    natural Brazilin    OBNB/OCNB                                                                             0.2     *yellow  yellow                                   C.I. Natural red 24                                                                       3:1                                                               C.I. No. 75280                                                                (H & W)                                                               natural Hematoxylin OBNB/OCNB                                                                             0.2     yellow   yellow                                   C.I. Natural Blk 1 & 2                                                                    3:1     0.05    yellow   yellow                                   C.I. No. 74290      0.005   yellow   yellow                                   (Baker)                                                               natural Morin       OBNB/OCNB                                                                             0.2     *yellow  yellow                                   C.I. Natural Yellow                                                                       3:1                                                               8, 11                                                                         C.I. No. 75660                                                                (B.D.H.)                                                              natural Diamond black                                                                             OBNB/OCNB                                                                             0.2     *greenish                                                                              greenish                                 C.I. Natural black 3 & 4                                                                  3:1                                                               C.I. No. 75291                                                                (ICN-K & K)                                                           natural Quercetin Dihydrate                                                                       OBNB/OCNB                                                                             0.2     *yellow  yellow                                   C.I. Natural yellow                                                                       3:1                                                               10, 13                                                                        C.I. Natural red 1                                                            C.I. No. 75670                                                                (Fluka)                                                               inorganic                                                                             New Green   OBNB/OCNB                                                                             0.2     dark green                                                                             dark green                       pigments                                                                              C.I. Pigment green 21                                                                     3:1     0.05    green    green                                    C.I. No. 77410      0.005   green    green                                    (ICN-K & K)                                                           inorganic                                                                             China Yellow                                                                              OBNB/OCNB                                                                             0.2     *dark yellow                                                                           dark yellow                              C.I. Pigment yellow                                                                       3:1     0.05    yellow   yellow                                   42, 43                                                                        C.I. Pigment brown                                                            6, 7                0.005   yellow   yellow                                   C.I. No. 77492                                                                (ICN-K & K)                                                           phenol- Tetrabromophenol                                                                          OBNB/OCNB                                                                             0.2     brownish yellow                                                                        brownish yellow                  phthaleine                                                                            phthalein ethyl                                                                           3:1     0.05    greenish yellow                                                                        greenish yellow                          ester               0.005   light green                                                                            light green                              (Eastman Kodak #6810)                                                 phenol- Tetrabromophenol                                                                          OBNB/OCNB                                                                             0.2     dark green                                                                             dark green                       phthaleine                                                                            phthalein ethyl                                                                           3:1     0.05    green    green                                    ester potassium     0.005   light green                                                                            light green                              salt                                                                          (Eastman Kodak #7083)                                                 disazo  44'bis(4-amino-1-                                                                         OBNB/OCNB                                                                             0.2     *greenish yellow                                                                       greenish yellow                          naphtylazo)-2,2'-                                                                         3:1                                                               stilbenedisulphonic                                                           acid                                                                          (Eastman Kodak #7089)                                                 unknown Solochrome Red B                                                                          OBNB/OCNB                                                                             0.2     *yellowish brown                                                                       yellowish brown                          (H & W)     3:1                                                       unknown Brenzcathechin                                                                            OBNB/OCNB                                                                             0.2     *very dark green                                                                       very dark green                          Violet      3:1                                                               (Merck)                                                               unknown 5(p-dimethyl                                                                              OBNB/OCNB                                                                             0.2     orange red                                                                             orange red                               aminobenzylidine                                                                          3:1     0.05    orange red                                                                             orange red                               rhodamine           0.005   orange yellow                                                                          orange yellow                            (Eastman Kodak #2748)                                                 __________________________________________________________________________     *not completely dissolved.                                               

EXAMPLE 13

The following Table 5 lists results of various compositions contrastingquick (instantaneous) versus slow (using ambient temperature) cooling ofliquids on color change:

                                      TABLE 5                                     __________________________________________________________________________                            % Concen-          Color                              Compound        Solvent tration                                                                             Liquid       Quick Cooling                                                                           Slow                     __________________________________________________________________________                                                         Cooling                  2,2'-(4,4'-Biphenylene)-                                                                      formamide                                                                             0.5   clear yellow white                              bis-(2-hydroxy-4,4'-di- 0.05  clear        white                              methylmorpholinuem Bromide)                                                                           0.005 clear        white                              (East. 9702)                                                                  Chicago Blue 6B Direct                                                                        formamide                                                                             0.5   navy blue    navy blue                          Blue 1 (MCB CX685)      0.05  royal blue   royal blue                                                                              royal blue                                       0.005 blue         light blue                         Aurintricarboxylic Acid                                                                       formamide                                                                             0.5   dark red     dark red                           (East. P 1946)          0.05  deep red     deep red  deep red                                         0.005 orange       orange-red                                                                              pink                     Cresyl violet perchlorate                                                                     formamide                                                                             0.5   deep purple w/red flourc.                                                                  deep purple                        (East. 11884)           0.05  pur. w/red flourc.                                                                         deep purple                                                0.005 blue w/red flourc.                                                                         violet                             Cresyl violet*  formamide                                                                             0.5   deep purple  deep purple                        Acetate (East. C8687)   0.05  bl (red flourc)                                                                            deep purple                                                0.005 lt. blue (red fl)                                                                          violet                             1,1'-Diethyl-2,2'*                                                                            formamide                                                                             0.5   aqua-blue    aqua-blue                          diarbocyanene Iodide    0.05  green-blue   green-blue                         (East. 9618)            0.005 lt. green blue                                                                             lt. green blue                     Chlorophenol red                                                                              formamide                                                                             0.5   yellow-orange                                                                              orange                             (East. 2116)            0.05  yellow-brown yellow-brown                                               0.005 brown green  brown green                        Chromotrope 2R* OBNB/OCNB                                                                             0.5   brown black  brown black                                                                             brown black              ICB CX 1620     3:1     0.05  dirty yellow dirty yellow                                                                            dirty yelow                                      0.005 yellow       yellow    yellow                   Erioglaucine* MCB EX 120                                                                      OBNB/OCNB                                                                             0.5   heather green                                                                              heather green                                                                           heather green                            3:1     0.05  green        light green                                                                             light green                                      0.005 lime green   lime green                                                                              lime green               New Fuchsia     OBNB/OCNB                                                                             0.5   purple       purple    purple                   MCB NX 280      3:1     0.05  violet       violet    violet                                           0.05  red          red       red                      Sudan II,       OBNB/OCNB                                                                             0.5   deep red orange                                                                            deep red orange                                                                         dp. red orange           MCB 2X1105      3:1     0.05  red orange   red orange                                                                              red orange                                       0.05  orange       orange    orange                   Oil Red EGN     OBNB/OCNB                                                                             0.5   dark red     dark red  dark red                 MCN OX160       3:1     0.05  deep red     deep red  deep red                                         0.05  red          red       red                      Eriochrome Cyanine R*                                                                         OBNB/OCNB                                                                             0.5   red-brown    red brown red brown                MCB EX105       3:1     0.05  brown yellow brown yellow                                                                            brown yellow                                     0.005 yellow       yellow    yellow                   Acridine Red*   OBNB/OCNB     Translucent-                                    PB A11000       3:1     0.5   hot pink     purple    purple                                           0.05  pink         red       red                                              0.005 peach        peach     peach                    Alizania Cyanine* Green                                                                       OBNB/OCNB                                                                             0.5   hunter green hunter green                                                                            hunter green             P & B A13170    3:1     0.05  lt. hunter green                                                                           lt. hunter green                                                                        lt. hunter green                                 0.005 lime green   lime green                                                                              lime green               Alizarin Yellow R*                                                                            OBNB/OCNB                                                                             0.5   muddy orange burnt orange                                                                            burnt orange             MCB AX505       3:1     0.05  deep yellow  deep yellow                                                                             deep yellow                                      0.005 yellow       yellow    yellow                   Orange IV*      OBNB/OCNB                                                                             0.5   muddy yl. brown                                                                            muddy yl. brown                                                                         muddy yl. brn.           MCB CK220       3:1     0.05  muddy yellow bright yellow                                                                           bright yellow                                    0.005 light yellow light yellow                                                                            light yellow             Janus Green     OBNB/OCNB                                                                             0.5   dark green-blue                                                                            dark green blue                                                                         dk green-blue            MCB JX10        3:1     0.05  green blue   green blue                                                                              green blue                                       0.005 hunter green green     green                    Rhodamine B,O   OBNB/OCNB                                                                             0.5   flourescent red                                                                            violet                             MCB RX75        3:1     0.05  floures. pink                                                                              deep lilac                                                 0.005 floures. pink                                                                              pale lilac                         Alizarin Blue*  OBNB/OCNB                                                                             0.5   dark green   grayish green                                                                           grayish green            Black B (MCB AX475)                                                                           3:1     0.05  dirty green  dirty green                                                                             dirty green                                      0.005 dirty yellow dirty yellow                                                                            dirty yellow             Indigo Synthetic*                                                                             OBNB/OCNB                                                                             0.5   black blue   black blue                                                                              black blue               MCB IX55        3:1     0.05  blue green   hunter green                                                                            blue green                                       0.005 aqua green   green     green                    Alizarin Yellow G, GG*                                                                        OBNB/OCNB                                                                             0.5   yellow-orange                                                                              yellow-orange                                                                           yellow orange            MCB AX500       3:1     0.05  yellow       yellow    yellow                                           0.005 light yellow light yellow                                                                            light yellow             Jenner Stain    OBNB/OCNB                                                                             0.5   deep purple  deep purple                                                                             deep purple              MCB JX15        3:1     0.05  purple       purple    purple                                           0.005 bluish purple                                                                              grayish purple                                                                          grayish purp.            Coomassie Brilliant Blue R                                                                    OBNB/OCNB                                                                             0.5   blue         green blue                                                                              green blue                               3:1     0.05  green        green     green                                            0.005 lime green   lime green                                                                              lime green               Chrysoidine Y,G*                                                                              OBNB/OCNB                                                                             0.5   reddish-brown                                                                              reddish brown                                                                           reddish brown            MCB CX 1650     3:1     0.05  burnt orange deep yellow                                                                             deep yellow                                      0.005 yellow       yellow    yellow                   Calmagite*      OBNB/OCNB                                                                             0.5   brown        brown     brown                    MCB CX323       3:1     0.05  light brown  light brown                                                                             light brown                                      0.005 yellow       yellow    yellow                   4,4'-Bis(dimethylamino)                                                                       OBNB/OCNB                                                                             0.5   orange       yellow-orange                                                                           orange-yellow            benzyhdrol (Eastman 1896)                                                                     75/25   0.05  yellow       bright dp. yl.                                                                          deep yellow                                      0.005 yellow       bright lt. yl.                                                                          light yellow             N--(p-Dimethylamine-                                                                          OBNB/OCNB                                                                             0.5   dark blue    deep blue dark blue                phenyl)-1,4 naptho-                                                                           75/25   0.05  deep blue    deep blue deep blue                quinoneimine (E. 478)   0.005 blue         light blue                                                                              light blue               Zinc Phtalocyanine                                                                            OBNB/OCNB                                                                             0.5   green brown  dark green                                                                              dark green               (E. 10030)      75/25   0.05  green        light green                                                                             light green                                      0.005 light yellow lt. greenish                                                                            lt. gr. yl.              N,N--Bis(p-butoxybenzylin-                                                                    OBNB/OCBN                                                                             0.5   yellow       yellow    yellow                   dene)-,α'-bi-p-toluidine                                                                75/25   0.05  yellow       yellow    yellow                   (E. 10576)              0.005 yellow       yelow     yellow                   Sudan Black B   OBNB/OCNB                                                                             0.5   deep blue    very dark blue                                                                          very dk blue             (E. C8690)      75/25   0.05  dark blue    very dark blue                                                                          very dk blue                                     0.005 dark blue    very dark blue                                                                          very dk blue             Sudan III       OBNB/OCNB                                                                             0.5   deep red     maroon    maroon                   (E. C1754)      75/25   0.05  red          red-brown reddish-brown                                    0.005 red          red-brown reddish-brown            Propyl Red      OBNB/OCNB                                                                             0.5   deep fushia  old rose                           (E. 944)        75/25   0.05  fushia       old rose                                                   0.005 fushia       rose                               2,4,6-Triphenyl-s-                                                                            OBNB/OCNB                                                                             0.5   bright yellow                                                                              bright yellow                                                                           bright yellow            triazine *(E. 10252)                                                                          75/25   0.05  bright yellow                                                                              bright yellow                                                                           bright yellow                                    0.005 bright yellow                                                                              bright yellow                                                                           bright yellow            Pyronin Y* (E. C8707)                                                                         OBNB/OCNB                                                                             0.5   pinkish purple                                                                             deep purple                                                                             deep purple                              75/25   0.05  reddish purple                                                                             maroon    maroon                                           0.005 reddish purple                                                                             maroon    maroon                   Xylene Cyanole, FF                                                                            OBNB/OCNB                                                                             0.5   blue-green   blue      blue                     *Technical      3:1     0.05  green (light)                                                                              light green                                                                             green                    (East. T1579)           0.005 green-yellow green-yellow                                                                            green-yellow             Coumarin 343    OBNB/OCNB                                                                             0.5   orange       orange    orange                   (East. 14943)   3:1     0.05  deep yellow  deep yellow                                                                             deep yellow                                      0.005 bright yellow                                                                              bright yellow                                                                           bright yellow            2,3,5-Triphenyl-2H--                                                                          OBNB/OCNB                                                                             0.5   yellow       yellow    yellow                   tetrazolium chloride                                                                          3:1     0.05  yellow       yellow    yellow                   (East. 6533)            0.005 yellow       yellow    yellow                   Toluylene Blue* OBNB/OCNB                                                                             0.5   dark gray blue                                                                             gray purple                        (ICN 18675)     3:1     0.05  dark green-blue                                                                            gray-purple                                                0.005 green        gray                               Coumarin 152    OBNB/OCNB                                                                             0.5   yellow, deep yellow, deep                                                                            yellow, deep             (East. 14369)   3:1     0.05  yellow       yellow    yellow                                           0.005 light yellow light yellow                                                                            light yellow             Wright's Stain  OBNB/OCNB                                                                             0.5   dark purple  dark purple                                                                             dark purple              (East. C8682)   3:1     0.05  purple       purple    purple                                           0.005 gray         gray      gray                     Cresyl Violet Perchloate                                                                      OBNB/OCNB                                                                             0.5   flourescent bl & red                                                                       dark purple                                                                             dark purple              (East. 11884)   3:1     0.05  flourescent bl & red                                                                       grayish purple                                                                          purple                                           0.005 flourescent green &                                                                        tan       green & red                                            red mixture                                     1,1'-Diethyl-2,2'-dicar-                                                                      OBNB/OCNB                                                                             0.5   dark green   blue purple                                                                             dark green               bocyanine Iodide                                                                              3:1     0.05  green        blue purple                                                                             green                    (East. 9618)            0.005 light green  lt. blue purple                                                                         light green              4,-Phenylaeodiphenyl-amine                                                                    OBNB/OCNB                                                                             0.5   orange       orange    orange                   (East. 1714)    3:1     0.05  deep yellow  deep yellow                                                                             deep yellow                                      0.005 light yellow yellow    yellow                   3,3'-Diethyloxadicarbo-                                                                       OBNB/OCNB                                                                             0.5   blue         purplish-blue                                                                           purplish-blue            cyanine Iodide  3:1     0.05  royal blue   blue      blue                     (East. 11219)           0.005 blue         lt. pur. blue                                                                           light blue               1,1',3,3,3',3'-Hexamethyl                                                                     OBNB/OCNB                                                                             0.5   dark green   metallic bl-gr                                                                          dark green               modtricarbocyanine Iodide                                                                     3:1     0.05  green        blue green                                                                              green                    (East. 14086)           0.005 light green  lt. blue-green                                                                          light green              Mendola' s Blue OBNB/OCNB                                                                             0.5   navy blue    purple    purple                   *(Pfaltz & Bauer No 4470)                                                                     3:1     0.05  blue         grayish purple                                                                          gray                                             0.005 light green  blue gray blue gray                3,3'-Diethylthiadicarbocy-                                                                    OBNB/OCNB                                                                             0.5   green blue   purple blue                                                                             navy blue                anine Iodide (East. 7663)                                                                     3:1     0.05  green blue   royal blue                                                                              blue                                             0.005 green        light blue                                                                              light green              Phosphine Dye   OBNB/OCNB                                                                             0.5   cherry red   rose      rose                     *(Pfaltz & Bauer P16810)                                                                      3:1     0.05  orange-red   pink      peach                                            0.005 light red    pink      peach                    Nitron (East. 1077)                                                                           OBNB/OCNB                                                                             0.5   reddish-brown                                                                              brown     brown                                    3:1     0.05  lt. yellow brn                                                                             golden tan                                                                              light brown                                      0.005 yellow       yellow    yellow                   Alizarin Cyanone                                                                              OBNB/OCNB                                                                             0.5   dark green   dark green                                                                              dark green               *(MCB AX480)    3:1     0.05  light green  light green                                                                             light green                                      0.005 yellow green yellow green                                                                            yellow green             Solvent Blue    OBNB/OCNB                                                                             0.5   blue         blue      blue                     (East. P9637)   3:1     0.05  green blue   green blue                                                                              green blue                                       0.005 light green  light green                                                                             light green              Chlorophenol Red                                                                              OBNB/OCNB                                                                             0.5   lt burnt orange                                                                            pink red  pinkish red              (East. 2116)    3:1     0.05  yellow       red       deep orange                                      0.005 light yellow pink      yellow                   Cresyl Violet Acetate                                                                         OBNB/OCNB                                                                             0.5   brown        purple    purple                   (East. C8687)   3:1     0.05  light brown  light purple                                                                            brown                                            0.005 orange yellow                                                                              silver tan                                                                              silver tan               Acid Cyanin     OBNB/OCNB                                                                             0.5   olive green  hunter green                                                                            hunter green             *(Pfalz & Bauer Al0770)                                                                       3:1     0.05  lt. olive green                                                                            light olive                                                                             light olive                                      0.005 yellow       yellow    yellow                   O--(2-a-(2-Hydroxy-5-sulfo-                                                                   OBNB/OCNB                                                                             0.5   purple       purple    purple                   phenylazo)benzylidene                                                                         3:1     0.05  light purple light purple                                                                            grayish purp.            hydrazine Benzoic Acid  0.005 dirty yellow dirty yellow                                                                            dirty yellow             Sodium Salt (East. 7199)                                                      Brilliant Cresyl blue                                                                         OBNB/OCNB                                                                             0.5   dark blue    dark purple blue                                                                        royal blue               (East. C1743)   3:1     0.05  blue         blue purple                                                                             blue                                             0.005 aqua-blue    purple    green                    P--Chloro-)-Toluidine                                                                         OBNB/OCNB                                                                             0.5   dark brown   dark brown                                                                              dark brown               Diazonium Chloride                                                                            3:1     0.05  hazel        gold      gold                     (Pfaltz & Bauer C19730) 0.005 yellow       yellow    yellow                   P--Naphtholbenzein                                                                            OBNB/OCNB                                                                             0.5   yellow       orange                             (East. 924)     3:1     0.05  orange       orange    or.                                              0.005 yellow       orange                             Fast Blue RR Salt                                                                             OBNB/OCNB                                                                             0.5   yellow-brown yellow-brown                                                                            yellow-brown             (Pfaltz & Bauer F00150)                                                                       3:1     0.05  yellow       yellow    yellow                                           0.005 light yellow light yellow                                                                            light yellow             Toluylene Orange*                                                                             OBNB/OCNB                                                                             0.5   orange yellow                                                                              orange-yellow                                                                           ornage-yellow                            3:1     0.05  yellow       yellow    yellow                                           0.005 light yellow light yellow                                                                            light yellow             Rose Bengal     Formamide                                                                             0.5   deep pink    dark red                           (East. C. 2245)         0.05  hot pink     hot pink                                                   0.005 pink         pink                               Hematein (stain)                                                                              Formamide                                                                             0.5   brown        brown                              (East. 2594)            0.05  deep brown   dark brown                                                 0.005 light brown  light brown                        Acid Alizarin Red B                                                                           Formamide                                                                             0.5   deep orange  deep red                           (ICN 10498)             0.05  orange       orange                                                     0.005 peach        peach                              5-Aminoflourescein                                                                            Formamide                                                                             0.5   deep yellow  orange-yellow                      (East. 10866)           0.05  yellow       yellow                                                     0.005 light yellow yellow                             8-Hydroxy-7-(6-Sulfo-2-                                                                       Formamide                                                                             0.5   deep orange-red                                                                            deep red                           naphthylazo) 5-Quinoline-                                                                             0.05  orange-red   orange-red                         sulfonic Acid Disodium  0.005 orange       orange                             Salt (East. 8643)                                                             Martius Yellow  Formamide                                                                             0.5   deep yellow  deep yellow                        (Pfaltz & Bauer M02390) 0.05  yellow       yellow                                                     0.005 light yellow yellow                             8-Hydroxy-1,3,6-Pyrenetri-                                                                    Formamide                                                                             0.5   milky-yellow yellow                             sulfonic Acid Trisodium 0.05  yellowish    milky white                                                                             milky white                                            milky-clear                                                             0.005 milky clear  white                              Alcian Blue 8GX Ingrain                                                                       Formamide                                                                             0.5   blue         royal blue                         Blue 1 MCB AX440        0.05  blue         blue      blue                     (East. 5180)            0.05  sky blue     sky blue                           Thianine Hydrochloride                                                                        Formamide                                                                             0.5   clear        white                                                      0.05  clear        white     clear white                                      0.005 clear        white                              Chlorantine Fast Red 5B                                                                       Formamide                                                                             0.5   cherry red   cherry red                                                                              cherry red               (Pfaltz & Bauer C07870) 0.05  deep red     deep red                                                   0.005 red-pink     pink                               Methylthymol Blue                                                                             Formamide                                                                             0.5   dk br yellow brown yellow                       (Est. 8068)             0.05  brownish yellow                                                                            brownish yellow                                                                         brownish yl.                                     0.005 yellow       light yellow                       __________________________________________________________________________     *denotes partly insoluble                                                

EXAMPLE 14

The following dyes in Table 6 were randomly mixed in the two solventslauric acid and 1-hexadecanol and observed for color changes:

                                      TABLE 6                                     __________________________________________________________________________               Lauric Acid          1-Hexadecanol                                 Compound   Liquid Fast   Slow   Liquid                                                                              Fast   Slow                             __________________________________________________________________________    Aurintricarboxylic                                                            Acid (East. P1946)                                                                       red-brown                                                                            light purple                                                                         light purple                                                                         red brown                                                                           peach  peach                            Acid Alizarin Red                                                             B (ICN IC490)                                                                            red    light red                                                                            light red                                                                            dark red                                                                            light pink                                                                           light pink                       8-Hydroxy-1,3,6                                                               syrene & Sulfonic                                                             Acid Trisodium Salt                                                           (East. 7281)                                                                             dp. yellow                                                                           lt. yellow                                                                           light yellow                                                                         totally insoluble                             5-Aminofluorescein                                                            (East. 10866)                                                                            lt. yellow                                                                           light tan                                                                            light tan                                                                            yellow                                                                              lt. orange                                                                           light orange                     Rose Bengal (Cert.)                                                                      burnt orange                                                                         rose   burnt orange                                                                         deep violet                                                                         deep violet                                                                          deep violet                      (East. 2 C2245)                 totally insoluble                             Martius Yellow                                                                (P & B MO2390)                                                                           orange yl.                                                                           deep yellow                                                                          deep yellow                                                                          yl. orange                                                                          light yellow                                                                         light yellow                     Chlorantine Fast Red                                                          5B (P & B C07870)                                                                        purple purple purple deep purple                                                                         light purple                                                                         light purple                     Methylthymol Blue                                                             (East. 8068)                                                                             peach  peach  peach  brown tan    tan                              8-Hydroxy 7(6-sulfo-                                                          2 naphthylazo)-5-                                                             quinoline sulfonic                                                            Acid Disodium Salt                                                                       TOTALLY INSOLUBLE                                                  Chicago Blue 6B                                                               (MCB CX 685)                                                                             gray black                                                                           gray   gray   gray black                                                                          gray   gray                             Alcian Blue 8GX                                                               (MCB AX410)                                                                              blue green                                                                           light blue                                                                           light blue                                                                           blue-green                                                                          light blue                                                                           light blue                       Thiamine                                                                      Hydrochloride                                                                            milky clear                                                                          white  white  milky clear                                                                         off white                                                                            off white                        (East. 5180)                                                                             Totally soluble                                                    __________________________________________________________________________

These dyes with the exception of those marked totally soluble were foundto be partially soluble in both solvents. Therefore any colors recordedwere not necessarily the true color of the dye in the solvent inproportional amounts.

Those dyes that were completely insoluble in both solvents were:

1. 2,2'-(4,4'-Biphenylene)-bis/2-hydroxy-4,4'-dimethyl-morpholinuimBromide) (East. 9762)

2. Henatein (stain) (East. 8594)

3. 8-Hydroxy-7-(6-sulfo-2-maphthi(azB)-5-quinoline-sulfonic AcidDisodium Salt (East. 8644)

The only dye that showed a significant color change was Rose Bengal(East. C2245) in Lauric Acid. Dilutions of this solution were made andthe following results were observed:

    ______________________________________                                                         Color                                                        Compound Solvent  % Conc.  Liquid  Fast  Slow                                 ______________________________________                                        Rose Bengal                                                                            Lauric   0.5      red-brown                                                                             rose  rose                                 (East. C2245)                                                                          Acid     0.05     lt. peach                                                                             pink  pink                                                   0.005    clear   white white                                ______________________________________                                    

                                      TABLE 7                                     __________________________________________________________________________                                % Recrystallized after cooling to                                Particle                                                                           Concentration                                                                         room temperature for 15 min.                                                                 -6° C. (cooling time)       Nucleating agent                                                                             size (m)                                                                           % (m/m) (after heating to 38° C.)                                                             after heating to 55°        __________________________________________________________________________                                               C.)                                Aerosil 380    10   0.1     6               86 (10 min)                       Lichrosorb RP8 (Merck,                                                        Germany) chemically                                                           modified silica                                                                              5    0.1     1               95 (10 min)                       399 magnesium silicate                                                                       5    0.1     0              100 (10 min)                       (Talc IT extra 5 micron)                                                      (Elvers Netherlands)                                                                              1       9              100 (10 min)                       (Whittaker, Clark & Daniels                                                   S. Plainfield, N.J.)                                                          Talc Mistron Super Frost                                                                          0.1     1              100 (10 min)                       (Cyprus Ind. Minerals Corp.)                                                                 2    1       1              100 (10 min)                                           2.5     0              100 (10 min)                                           5       3              100 (10 min)                       Boron, amorphoos                                                              (Starck, Germany)                                                                            0.05 0.1     3               93 (40 min)                       Titanium carbide                                                              (Starck, Germany)                                                                            0.05 0.1     2              100 (20 min)                       Diamond (Spring A.G.,                                                         Switzerland)   2-4  0.1     1               95 (20 min)                       Boron, crystalline                                                            (Starck, Germany)                                                                            0.05 0.1     1               98 (20 min)                       Molybdenium disulphide                                                        (Fluka A.G., Switzerland)                                                                    abt. 10                                                                            0.1     1               95 (10 min)                       Alumina (Tonerde)                                                             (Dujardin, Germany)                                                                          0.25 0.1     0              100 (10 min)                       Porous alumina                                                                (Lichrosorb Alox T)                                                                          5    0.1     0              100 (20 min)                       none           --   --      2               30 (10 min)                                                                   46 (60 min)                       __________________________________________________________________________

EXAMPLE 15

This example demonstrates the use of insoluble nucleating agents in atemperature-indicating device in order to render the composition ofmatter recrystallizable at a predetermined temperature.

A number of cavities formed in an aluminium carrier layer were filledwith a mixture of ortho-bromonitrobenzene and ortho-chloronitrobenzene(mass ratio 3:1), containing 0.025 mass % of pinacyanol iodide to whichdifferent amounts of nucleating agents had been added. The cavities thusfilled were provided with a heat-sensitive transparent Surlyn 1652 film(E. I. DuPont de Nemours & Company) laminated to a polyester film(Melinex ICI).

After recrystallization of the chemicals at -40° C., the indicatingdevice was heated for one hour at about 55° C. (imitation of storage athigh temperatures).

The indicating device was cooled at -6° C. and the percentage ofcavities in which the mixture has recrystallized was determined.

In a second series the indicating device containing recrystallizedmixture, was heated in a water bath for 45 seconds just above themelting point of the chemicals (abt. 38° C.) in order to imitate ameasurement of the temperature of the human body.

Then the indicating device was cooled to room temperature and thepercentage of cavities in which the chemicals has crystallized wasdetermined.

For comparison, cavities were filled with the same OBNB/OCNB mixturecontaining 0.025 mass % pinacyanol iodide but without nucleating agents.

The results are presented in Table 7.

It appears that whereas the addition of a nucleating agent favorablyinfluences the recrystallization at -6° C., it does not affect theundercooling at room temperature.

EXAMPLE 16

This Example demonstrates the use of a pretreated aluminum carrier layerfor rendering the compositions of matter recrystalizable at apredetermined temperature. An aluminum carrier layer provided withcavities was passivate by cleaning the aluminum with acetone, picklingin a 2% solution of sodium hydroxide, subsequent pickling in 10% nitricacid and immersion in boiling water for 5 minutes. The cavities werefilled with a mixture of ortho-chloranitrobenzene andortho-bromonitrobenzene (mass ratio 1:3) containing 0.025 mass % ofpinacyanol iodide. The filled cavities were further treated as describedin Example IX. For comparison, cavities formed in untreated aluminumwere filled with the above-mentioned mixture and treated in a similarway.

The results are given in Table 7A

                  TABLE 7a                                                        ______________________________________                                               % Recrystallized after cooling to                                               room temperature for                                                                         -6° C. (cooling time)                                   15 min (after heating                                                                        after heating to                                      Treatment                                                                              to 38° C.)                                                                            55° C.)                                        ______________________________________                                        none     2              30 (10 min)                                                                   46 (60 min)                                           passivation                                                                            about 5        100 (30 min)                                          ______________________________________                                    

It appears that the passivation of the aluminum carrier layer favorablyinfluences recrystallization at -6° C.

EXAMPLE 17

A transparent polyester film (Melinex, supplied by ICT provided with anadhesive layer of polyisobutylene is pressed together with an aluminumlayer foil. As a measure of the adhesive strength is taken, the force ing/cm which is requred to peel the polyester film off the aluminum foilat a rate of 30 cm/minute. This force should be at least about 150 g/cm.

The influence on the magnitude of the peeling force has beeninvestigated of the nature of the aluminum surface (rough, smooth,etched), the type of polyisobutylene (molecular weight, mixture) andbonding pressure (5 and 50 kg/cm²).

The polyisobutylene types used have been obtained from BASF,Ludwigshafen, W. Germany and are marketed under the trade name Oppanol.The results are listed in Table 9.

                                      TABLE 9                                     __________________________________________________________________________            Peeling force in g/cm                                                 Pretreatment of                                                                       PIB1  PIB2  PIB3  PIB4  PIB5                                          aluminium foil                                                                        A  B  A  B  A  B  A  B  A  B                                          __________________________________________________________________________    Rough surface 1                                                                       550                                                                              600                                                                              400                                                                              600                                                                              100                                                                              150                                                                               20                                                                               20                                                                              400                                                                              450                                        Smooth surface                                                                        600                                                                              600                                                                              600                                                                              600                                                                              150                                                                              200                                                                              100                                                                              130                                                                              400                                                                              450                                        etched:                                                                       Rough surface 2                                                                       600                                                                              600                                                                              600                                                                              600                                                                              100                                                                              240                                                                               40                                                                              120                                                                              -- --                                         Smooth surface                                                                        600                                                                              600                                                                              600                                                                              600                                                                              250                                                                              330                                                                              200                                                                              300                                                                              -- --                                         coated:                                                                       Rough surface 3                                                                       400                                                                              400                                                                              400                                                                              400                                                                              400                                                                              400                                                                              400                                                                              400                                                                              -- --                                         Smooth surface                                                                        300                                                                              300                                                                              300                                                                              300                                                                              300                                                                              300                                                                              300                                                                              300                                                                              -- --                                         __________________________________________________________________________     A = used bonding force 5 kg/cm.sup.2                                          B = used bonding force 50 kg/cm.sup.2                                         1 rough surface: mechanically roughened;                                      2 etched: pretreatment with a solution of sodium metasilicate in water;       3 coated: surface layer Oppanol B 150, thickness 5μ.                       PIB1: Oppanol B15, average mol. wt. 77-92.10.sup.3 ;                          PIB2: Oppanol D3061, average mol. wt. about 140.10.sup.3 ;                    PIB3: Oppanol B50, average mol. wt. 340-480.10.sup.3 ;                        PIB4: Oppanol B150, average mol. wt. 2.3-3.3.10.sup.6 ;                       PIB5: mixture of Oppanol B15/B150 (1:1).                                 

EXAMPLE 18

Of polyisobutylene the permeability is investigated for the chemicalsused in the temperature-indicating device. Polyisobutylene films areformed from a solution disposed on paper. The films thus obtained aremade into bags of about 60 cm which are filled with 2.5 grams of amixture of ortho-chloronitrobenzene and ortho-bromonitrobenzene (weightratio 62:38) and sealed. After being weighed, the bags are stored at 32°C. in a room with air circulation and after different periods the lossof weight is determined.

The results are summarized in Table 10.

                  TABLE 10                                                        ______________________________________                                        Sample         Loss of weight in mg/h/μ/cm.sup.2                           ______________________________________                                        PIB1           0.12                                                           PIB2           0.14                                                           PIB3           0.17                                                           Surlyn 1652 (control)                                                                        1.05                                                           ______________________________________                                    

The designations PIB1, PIB2 and PIB3 have the same meaning as in ExampleXV. For comparison, mention is made of the result obtained with a film(thickness about 45μ) of an ionimeric adhesive Surlyn 1652. It appearsthat the polysobutylene samples are far less permeable than theionomeric adhesive. cl EXAMPLE 19

Cavities formed in an aluminium carrier layer are filled with mixturesof ortho-chloronitrobenzene and ortho-bromonitrobenzene and sealed witha cover layer of polyester film provided with a polyisobutylene adhesivelayer. The test objects thus obtained are stored at 20° C. and 32° C.and examined under a stereo microscope to establish whether thechemicals dissolve in the adhesive layer disappear from their cavitiesor become liquid.

Observations were taken for 40 days. The results are given in Table 11.

                  TABLE 11                                                        ______________________________________                                        Sample                                                                              Observations                                                            ______________________________________                                        PIB1  After a few days viscous deformation of the glue layer                        occurs at 20° C.                                                       No leaking away or dissolving of the chemicals after 40                       days at 32° C.                                                   PIB2  No leaking away or dissolving of the chemicals after 40                       days at 32° C.                                                   PIB3  After a few days slight viscous deformation of the                            polyisobutylene occurs at 20° C. At the end of the                     observation period some leaking away of chemicals as a                        result of the polyisobutylene becoming detached from                          the aluminium.                                                          PIB4  After 40 days at 32° C. no viscous deformation occurs.                 No leaking away or dissolving of chemicals in those                           places where the adhesion between aluminium and poly-                         isobutylene has been maintained. In a few places the                          polyisobutylene layer has become detached from the                            aluminium and chemicals have leaked away there.                         ______________________________________                                    

From this table is appears that the chemicals neither leak away nordissolve, provided that the adhesion to the aluminium foil is kept up.

High molecular weight polyisobutylene (PIB4) is the least liable toviscous deformation.

EXAMPLE 20

In this example, the reproducibility of the temperature indication isdemonstrated. A number of cavities formed in an aluminum carrier layerare filled with a series of mixtures of ortho-chloronitrobenzene,ortho-bromonitrobenzene and 0.1% by weight of orasol blue BLN (solventblue 49), whose melting temperatures progressively increase by 0.1° C.The cavities thus filled are covered with Whatman chromatography paperNo. 1 and subsequently sealed with a polyester film (Melinex) providedwith a pressure-sensitive adhesive layer of polyisobutylene. Thepolyisobuytlene used is a mixture of equal parts of Oppanol B15 (averagemolecular weight 77,000-92,000) and Oppanol B100 (average molecularweight 1.08-1.46×10⁶). The test objects are stored at 28° C. and after3, 7 and 10 weeks, respectively, placed in a water bath of a particulartemperature to measure the temperature at which discoloration of theindicator layer takes place.

The results obtained as average values of the 4 temperature indicatingdevices are listed in Table 12.

                  TABLE 12                                                        ______________________________________                                                   Temperature at which                                                          discoloration occurs (°C.)                                  ______________________________________                                        After 0 weeks                                                                              36.40                                                            3 weeks      36.45                                                            7 weeks      36.48                                                            10 weeks     36.50                                                            ______________________________________                                    

It appears that the temperature indication as a function of time doesnot or hardly undergo any change.

EXAMPLE 21 (comparative)

A number of known adhesives with which an adhesive layer can be formedat room temperature are examined in the way described in Example XIX.The aluminium foil used has previously been etched. From the resultsummarized in Table 13 it apppears that of the adhesives examined, whichall fall beyond the scope of the present invention, none are suitable tobe used for the present purpose envisaged.

                                      TABLE 13                                    __________________________________________________________________________                        Curing or                                                               Cover drying time                                               Adhesive Solvent                                                                            layer (min) Observations                                        __________________________________________________________________________    Epoxide coating                                                                        none polyester                                                                           3-14  Influence of curing time:                           thickness 10               3-6 min: chemicals turn liquid;                    Ceta Bever                13-14 min: poor adhesion to aluminum;                                          3-13 min: after 2 days at 32° C.                                      chemicals                                                                          have dissappeared (dissolved                                                  in adhesive layer).                            Epoxide, coating                                                                       none polyester                                                                           5-45  Influence of curing time:                           thickness 10               5-25 min: chemicals turn liquid;                   Araldite                  25-35 min: after 4 days at 20° C.            Ciba-Geigy                     yellowing and disappearing                                                    of chemicals.                                  Bi-component                                                                           methyl-                                                                            polyester                                                                           solvent                                                                             Influence of dying time:                            polyurethane                                                                           ethyl      evaporated                                                                          2.5-4.5 hours: after 4 days at 32° C.        Adcote 301A/350                                                                        ketone     at 50° C.                                                                           chemicals disappear;                         Morton-Williams             4.5 hours: poor adhesion to                       PUR 2837,                        aluminium.                                   Ciba-Geigy                                                                    Silicone RTV 108                                                                       none cellophane                                                                          0-45   0-30 min: chemicals turn liquid;                   General Electric            45 min: poor adhesion to aluminium;               is affected by            30-45 min: after 7 days at 20° C.            moisture                       chemicals disappear                            Silgrip 574                                                                            none polyester                                                                           none  After 3 days at 20° C.: chemicals turn       General Electric          liquid and dissolve in the glue layer               pressure-sensitive                                                            glue (silicones)                                                              Polyvinyl alcohol                                                                      water                                                                              cellophane                                                                          solvent                                                                             After the waater had been entirely                  Elvanol 71-30       evaporated                                                                          removed, adhesion between polyvinyl                 DuPont              at 20° C.                                                                    alcohol and aluminium was insufficient                                        with all psamples.                                  __________________________________________________________________________

Suppliers of dyes used in our invention:

Eastman Kodak (E.K.) Rochester, N.Y.

acridine yellow, Azure A™, B™ and C™,4,4'bis(2-amino-1-naphthylazo)-2,2'-stilbene disulfonic acid,4,4'-bis(4-amino-1-naphtylazo)-2,2'-stilbene disulfonic acid, quinaldinered, Chlorasol Black E™, 4,5'-dibromofluorescein,1,1-diethyl-2,2'-cyanine iodide, 5-(p-dimethylaminobenzylidine)rhodamine, p-(p-dimethylaminophenylazo)-benzenoic acid sodium salt,4-(4-dimethylamino-1-naphthylazo)-3-methoxybenzene-sulfonic acid,2-(p-dimethylaminostyryl)-1-ethyl-pyriolinium iodide,4-(p-ethoxyphenylazo)-bis-phenylenediamine monohydrochloride, EthylEosin™, Gallein™, Methylene Violet™, Naphthol Yellow S™, Nile blue A™

Merck 6100 Darmstadt, W. Germany

acridine orange, Alizarine Yellow GG™, Alizarine Yellow R™, alizarinesulfonic acid sodium salt, alkali blue, amaranth, auramine,aurintricarboxylic acid ammonium salt, Azarcarmine B™, benzyl orange,Brilliant Cresyl Blue™, Calcon™, chlorophenol red, Diamine Green B™,fast yellow, Eriochrome Cyanine R™, Evans Blue™, phloxine, fuchsin,fuchsin NB™, yellow orange S™, cresol red, curcumin, methyl green,methyl red sodium salt, murexide, Orange GGN™, Patent Blue V™, Ponceau6R, Rhodamine B™, Rhodamine 6G™, safranin, Salicyl Yellow™, ThioflavineTCN™, thionin, Trypan Blue™

Matheson, Coleman & Bell (M.C.&B.) Box 85, E. Rutherford, N.J. acridinered, Alizarine Blue Black B™, Aniline Yellow™, Anthraquinone Violet R™,Benzo Fast Pink 2 BL™, Benzopurpurin 4B™, quinoline yellow (spiritsoluble), Chromolan Yellow™, Crocein Scarlet MOO, 3B™, fast yellow, FastGreen G™, Fast Green FCF™, Erichrome Black A™, Erythrosin YellowishBlend™, ethylviolet, methyl violet base, Naphthalene Green V™, Oil RedEGN™, Patent Blue™, Ponceau G, R, 2R™, Ponceau 3R™, prussian blue,resorsin brown, Victoria Blue R™

ICN--K&K 121 Express St., Plainview, N.Y.

acridlavine, Alizarine Brilliant Blue BS™, alizarine viridin, amethystviolet, Bindschedler's Green™, Capri Blue™, celestine blue, chinayellow, ciba blue, Coriphosphine O™, Cyanosin B™, diamond black,Eriochrome Blue SE™, 4-phenylazo-1-naphthylamine, phenylene blue,gallamine blue, Gallocyanine™, induline, (alcohol or water soluble),Iris Blue, magdala red, neutral red (iodide), neutral violet, new green,Oil Blue N™, proflavine, resazurin, rhoduline violet, rivanol, solwaypurple, Thioindigo Red™, Violamine 3B™, Acid Alizarine Blue BB™

Fluka, CH-9470 Buchs, Switzerland

alizarine, aurankia, azophloxine, Azocarmine g™, Bismarck brown G™,Bismarck Brown R™, brilliant green, quinalizarin, quinoline yellow,Chromazurol S™, Chromotrope 2B™, Chrysoidine G™, Chrysoidine R™,dichlorofluorescein, Fast Violet Salt, Eosin Yellowish, Eosin Scarlet,Eriochrome Blue Black B™, Eriochrome Red B™, Erythrosin Extra Bluish™,Indigo Synthetic™, induline (water soluble), Light Green SF yellowish™,methylene green, Naphthol Blue Black B™, 2-nitroso-1-naphthol,1-nitroso-2-naphthol, Orange I™, Orange II™, Orange G™, parafuchsine,Ponceau BS™, Ponceau S™, Pyronin G™, quercetin dihydrate, Scarlet R™,SNADNS, Sudan III™, Thiazine Red R™, Fat Black, Victoria Blue B™, Waterblue, acid fuchsin, Fast Red Salt RC and B and 3GL™, Fast Blue Salt BBand B™, Fast Garnet Salt GBC™

Hopkins & Williams (H&W) St. Cross Street, London, England

Alizarine Blue S™, Alizarine Cyanine 2R™, alkanin, Anthracene Blue 2R™,anthrapurpurin, brazilin, Chromotrope 2R™, purpurin, rosolic acid

Carl Roth, Postfach 210980, D-7500 Karlsruhe, W. Germany

quercitrin dihydrate

Baker, Postbus 1, Deventer, Netherlands

Alizarin Red S™, Alkali Blue 6B™, bromophenol blue, bromocresol green,bromocresol purple, Eriochrome Black T™, phenosafranin, hematoxyline,indigo carmine, metanil yellow, methylene blue, methyl orange, NaphtholGreen B™, neutral red (chloride), Oil Red O™, Orange IV™, Rhodamine Bbase™, Sudan III™, Tropaeolin O™, Xylene Cyanol FF™, congo red

Y. D. Towers & Co. LIverpool, England

malachite green

Serva, Heidelberg, W. Germany

Toluidine Blue O™

Sandoz, Basle, Switzerland

Artisil Yellow F-L™, Carta Yellow G 180 o/o™, Sandorin Bordeaux 2RL™,Sandorin Green GLS™, Sandorin Violet BL™, Savinyl Blue B™, Savinyl BlueGLS™, Savinyl Blue RS™, Savinyl Green B™, Savinyl Red BLSN, Savinyl FireRed 3 GLS™, Solar Turquoise Blue GGL 160 o/o™

I. G. Farben Frankfurt A.M., Germany

Rose Bengal™, tartrazin

Holliday Frankfurt A.M., Germany

brilliant ponceau 5R

BASF Ludwigshafen, W. Germany

Celliton Blue Extra™, Celliton Fast Blue FFG™, Sudan red G™

Bayer Leverkusen, W. Germany Ceres Blue R™, Ceres Yellow 3R™, CeresOrange R™, Ceres Red B™

Koninklyke pharmaceutische Fabriek, Stationswig 39/41, Meppel,Netherlands

cochenille

Ciba-Geigy, Basle, Switzerland

Cromophthal Blue A3R™, Cromophthal Boroleaux RS™, Cromophthol Red A3B™,Irgalith Blue GLSM™, Irgalith Blue TNC™, Irgalith Green BLN™, IrgalithGreen DBN™, Irgalith Magenta TCM™, Irgalith Red P4R™, Irgalith PinkTYNC™, Irgalith Violet MNC™, Orasol Blue BLN™, Orasol Blue 2GLN™, OrasolBrilliant Blue GN™, Orasol Navy Blue 2RB™, Orasol Orange RLN™, OrasolRed G™, Solophenyl Brilliant Blue BL™, Solophenyl Red 3BL™, SolophenylTurquois Blue GRL™, Terasil Yellow 2GW™

American Cyanamid Bound Brook, N.J.

D & C Green 6™

Ciba T Basle, Switzerland

Deorlene blue 5G™

Amsterdamsche Clininefabrick (A.C.F.) Amsterdam, Netherlands

Dimethyl yellow, crystal violet, methyl violet, Tropaeolin OO™

Geigy Basle, Switzerland

Eriochrome Azurol B™

British Drug Houses (B.D.H.) Poole, Dorset, England

Erioglaucine, Janus Green, morin, Titanium Yellow

Edward Gurr, 42 Upper Richmond Rd., London, England

nigrosine, Sudan Red 7B™

Sandoz, Basle, Switzerland

Nitro Fast Blue 3GDB™, Nitro Fast Green GSB™, Fat Red BS™

Ugine Kuhlmann, Paris, France

Organol Blue VIFYN™, Organol Yellow GR™, Organol Orange 2R™

Miscellaneous

brilliant yellow

cryptocyanine*

phloxine B*

fluourescein sodium salt (prepared from Merck fluorescein)

phthalocyanine*

These dyes may be obtained through local suppliers, including EastmanKodak.

EXAMPLE 22

In a further preferred embodiment for the clinical thermometers of theinvention, one of the novel compositions of matter is solidified, groundto a very fine powder, and dispersed in a solution of polymer resin. Apreferable polmyer resin is polyvinyl alcohol.

The polymer resin is selected based upon (1) compatability with thenovel temperature-indicating composition of matter, and (2) by thenon-solubility of the temperature-sensing composition of matter ineither the resin or the solvent for the resin. All components of thenovel temperature-indicating composition of matter must be insoluble inthe resin and in the resin and solvent. A preferred example is a systemwhich uses polyvinyl alcohol for the polymer resins, water as a solvent,and novel composition of matter consisting ofortho-bromonitrobenzene/ortho-chloronitrobenzene solid solution withpinacyanol iodide added to the ortho-bromonitrobenzene andorth-chloronitrobenzene as hereinbefore described.

For some applications it is desirable to have a temperature-indicatingcomposition which is easily reversible. Such a reversible compositionnature can be obtained by mixing a suitable nucleating agent, preferablytalc, with the novel compositions of matter before solidifying andgrinding, or by dispersing the nucleating agent in the resin solutionseparately from the novel composition of matter particles.

For some applications such as human clinical temperature taking, it isdesirable to prevent the patient's saliva from dissolving the polyvinylalcohol or other water-soluble polymer resin. This can be accomplishedby applying a layer of pressure sensitive composition packages or byapplying a separate coating of polymer resin which is not water soluble.

In any event, the dispersed solution is deposited on an aluminum orplastic backing sheet, which may or may not have pockets, after whichthe water of the solution is evaporated, leaving a water-soluble mass ofpolymer with dispersed novel composition of matter particlestherewithin.

The advantages of using such a novel composition temperature sensingpackage are as follows: first, the display in a cavity such as FIG. 7is, from above, a full circle of color, but also the dispersed solutioncan be applied in other geometry's to form messages, words, numbers andthe like. Another advantage is that the system is very insusceptible tonucleation occurring in the supercooled liquid. This is because withineach dot of a matrix thermometer there are thousands of small pools ofsuper-cooled liquid, each one separate from the other. A nucleationevent occurring in one pool of chemical does not affect the other poolsof chemical. Thus the indication of temperature is much more stable andcontrollable than in those systems which utilize one large pool of novelcomposition of matter for each point on the matrix of the thermometer.

In order to utilize these novel composition of matter packages toconstruct the thermometer, it is necessary to provide a means fordepositng very small quantities of this material onto the backing. Sucha system as is currently used in thermomoeter machines known to those inthe art. Such a system for applying the dispersed solution to a templatehaving cavities such as backing 44 of FIG. 12 consists of a syringe pumpsuch as a Sage model 371 syringe (Sage Instruments Inc., Div of OrionResearch Corp., Cambridge, Mass.) pump. The output of the syringe pumpis directed through tubing to a fill head as previously described. TheSage syringe pump output rate is adjusted by changing gears, motorspeed, etc., until the output of the pump equals the uptake of thebacking material. In operation, the flow of the material would becontinuous and at the fill tip a small droplet of material would beginto form at the start of each cycle. The droplet would grow in size, butwould be smaller in size than would be required for gravity acting uponthe droplet to cause the drops to fall off. As the filling cyclecontinues, the filling head is brought very close to the backingmaterial and the growing droplet touches the backing material, wets thebacking material, and the fluid flows off the pin. The fill cyclecontinues as the head is raised away from the backing material and thegrowth of a new droplet begins to take place on each fill pin.

EXAMPLE 23

In yet another preferred embodiment, a polymeric resin, generally awater-soluble polymeric resin, is applied as a coating film to the topof pockets (58 of FIG. 13) which have already been partially filled withthe novel compositions of matter. The thermometer is then allowed tostand until all the solvent has evaporated away. As a further preferredembodiment, a covering pressure sensitive adhesive tape can be appliedon top of the coating.

The preferred polymer material for casting upon the thermometer is awater soluble polymer such as polyvinyl alcohol (99 to 100% hydrolized).The solvent for polyvinyl alcohol is water. A second preferred polymerresin is polyisobutylene cast from a solution of aliphatic hydrocarbonsolvent.

The covering pressure sensitive adhesive tape can be a polyisobutylenecoated polyester or the like or Permacel's J-Lar 910™ (The Permacel Co.,New Brunswick, N. J., a division of Johnson & Johnson). The pressuresensitive adhesive tape covering provides additional strength anddurability protecting the coating covering the film from disruption andabrasion. Also in applications for human clinical thermometry, thecovering layer of pressure sensitive adhesive tape prevents the watersoluble resins such as polyvinyl alcohol from dissolving in thepatient's saliva or in the water used in test bath apparatus.

It has also been found that such a thermometer has vastly improvedregenerative properties when a nucleating agent for the novelcomposition of matter is added to the solution of coating resin. Thus,then the novel composition of matter is pinacyanol iodide dissolved inortho-bromonitrobenzene:orthochloronitrobenzene solid solutions, thenucleating agent talc (Whittaker, Clark & Daniels, South Plainfield, N.J. #399 magnesium silicate) is added to the solution of the coatingresin before application to the thermometer. The thermometers made inthis fashion will show complete recrystallization within 18 hours at 0°C. Thermometers constructed as above but without addition of talc willhave only about 25% of the pockets recrystallized within 18 hours at 0°C.

EXAMPLE 24

The following Table gives further results of possible Group IIIcompounds:

                                      TABLE 14                                    __________________________________________________________________________                           % Concen-                                                                           Color                                            Compound      Solvent tration                                                                             Liquid  Quick Cooling                                                                         Slow Cooling                      __________________________________________________________________________    Jenner Stain MCB JX15                                                                       OBNB/OCNB                                                                             0.5   deep purple                                                                           deep purple                                                                           deep purple                                     3:1     0.05  purple  purple  purple                                                  0.005 bluish purple                                                                         grayish purple                                                                        grayish pur.                      Coomassie Brilliant Blue R                                                                  OBNB/OCNB                                                                             0.5   blue    green blue                                                                            green blue                                      3:1     0.05  green   green   green                                                   0.005 lime green                                                                            lime green                                                                            lime green                        Chrysoidine Y, G*                                                                           OBNB/OCNB                                                                             0.5   reddish-brown                                                                         reddish-brown                                                                         reddish-brown                     MCB CX 1650   3:1     0.05  burnt orange                                                                          deep yellow                                                                           deep yellow                                             0.005 yellow  yellow  yellow                            Calmagite* MCB CX323                                                                        OBNB/OCNB                                                                             0.5   brown   brown   brown                                           3:1     0.05  light brown                                                                           light brown                                                                           light brown                                             0.005 yellow  yellow  yellow                            Azure A Bosinate*                                                                           OBNB/OCNB                                                                             0.5   blue    purple blue                                                                           dark purple                       MCB AX 1880   3:1     0.05  blue    purple blue                                                                           purple                                                  0.005 blue    grayish purple                                                                        grayish pur.                      Celestine Blue*                                                                             OBNB/OCNB                                                                             0.5   dk. blue-green                                                                        drab blue                                                                             olive green                       MCB CX573     3:1     0.05  blue    blue    dk. gr-blue                                             0.005 lt. blue-green                                                                        lime green                                                                            blue-green                        Methyl Violet 2B                                                                            OBNB/OCNB                                                                             0.5   royal blue                                                                            purple  purple                            MCB MX 1545   3:1     0.05  navy blue                                                                             purple  royal blue                                              0.005 blue    blue purple                                                                           blue                              Rhodamine 6G  OBNB/OCNB                                                                             0.5   dk. fluorescent                                                                       deep raspberry                                                                        deep rose                                       3:1     0.05  pink    raspberry                                                                             rose                                                    0.005 orange  orange  orange                            Methylene Green                                                                             OBNB/OCNB                                                                             0.5   dk. green-blue                                                                        dk. navy blue                             MCB MX1020    3:1     0.05  green blue                                                                            green blue                                                      0.005 bluish green                                                                          green                                     Crystal Violet                                                                              OBNB/OCNB                                                                             0.5   royal blue                                                                            purple  purple                            MCB CX2095    3:1     0.05  navy blue                                                                             purple  purple                                                  0.005 blue    purple  purple                            Gentian Violet                                                                              OBNB/OCNB                                                                             0.5   royal blue                                                                            purple  purple                            MCB GX55      3:1     0.05  navy blue                                                                             purple  purple                                                  0.005 blue    pink purple                                                                           pink purple                       Azure B       OBNB/OCNB                                                                             0.5   dk. green blue                                                                        purple  purple                            MCB AX1885    3:1     0.05  green blue                                                                            purplish blue                                                                         purple blue                                             0.005 green   pale greyish pur.                                                                     green                             Methylene Blue                                                                              OBNB/OCNB                                                                             0.5   deep blue                                                                             indigo                                                  3:1     0.05  greenish blue                                                                         purple blue                                                     0.005 green   lt. purplish blue                                       OBNB/OCNB                                                                             0.5                                                                   3:1     0.05                                                                          0.005                                                                 OBNB/OCNB                                                                             0.5                                                                   3:1     0.05                                                                          0.005                                                   Methylene Blue                                                                              OBNB/OCNB                                                                             0.5                                                                   3:1     0.05                                                                          0.005                                                                 OBNB/OCNB                                                                             0.5                                                                   3:1     0.05                                                                          0.005                                                                 OBNB/OCNB                                                                             0.5                                                                   3:1     0.05                                                                          0.005                                                                 OBNB/OCNB                                                                             0.5                                                                   3:1     0.05                                                                          0.005                                                                 OBNB/OCNB                                                                             0.5                                                                   3:1     0.05                                                                          0.005                                                   __________________________________________________________________________

We claim as our invention:
 1. A composition of matter exhibiting a sharpcolor change upon transition from a liquid state to a solid state orfrom a solid state to a liquid state, capable of being supercooled forat least several minutes, and substantially free of impurities, to forma solid solution when the composition is in a solid state, consistingessentially of:(a) a solvent adapted to change from a solid state atsubstantially a predetermined temperature to a liquid state; and (b) aneffective amount of an indicator material selected from the groupconsisting of pinacyanol iodide, thionin, methylene blue, cresol red,neutral red iodide, neutral red chloride, crystal violet, acridinorange, Orasol Orange RLN™, Orasol Navy Blue ™, Irgalith Red PR™, FatRed BS™, Xylene Cyanol FF™, Rhodamine B™, Rhodamine 6G™, IrgalithMagenta TCB™, Irgalith Pink TYNC™, Toluidene Blue O™, Savinyl Green B™,Savinyl Blue RS™, purpurin, 3,3'-diethylthiadicarbocyanine iodide,cryptocyanine, Dicyanine A™, Merocyanine 540™,4-(p-ethoxyphenylazo)-m-phenylene diamine hydrochloride, Yellow OrangeS™, Chrysoidan G™, fuchsin, aurintricarboxylic acid (ammonium salt),Victoria Blue R™, Pyronin G™, gallein, Erythrosin Yellow Blend™,chlorophenol blue, bromophenol blue, bromocresol purple, CoriphosphineO™, acriflavine, acridine orange, rhoduline violet, Alizarin Cyanine2R™, Alizarin Red S™, alcannin, Aurantia, Direct Green G™, Fast Salt Red3GL™, Fast Salt Blue BB™, Fast Garnet Salt GBC™, Carta Yellow G 1800/0™, murexide, Savinyl Blue GLS™, Irgalith Blue GLSM™, phthalocyanine,Di Amingreen B™, Alizarin Blue S™, Celliton Blue Extra™ , neocyanine,Janus Green™, dimethyl yellow, Fast Yellow™, methyl red sodium salt,Alizarin Yellow R™, Eriochrome Black T™, Chromotrope 2R™, Ponceau 6R™,Brilliant Ponceau G/R/2R™, chromolan yellow, Sudan Red B™, Bismark brownG™, Fat Black™, Resorcin Brown™, Benzofast Pink 2BL™, Oil Red EGN™,Euroglaucine, Fuchsin NB™, parafuchsin, Patent Blue™, Irgalith BlueTNC™, Phloxin B™, fluorescein sodium salt, Rhodamine B base™, EosinScarlet, Eosin Yellowish, Erythrosin extra bluish,4,5-dibromofluorescein, ethyleosin, Phloxin™, Cyanovin B™, chlorocresolgreen, pinacyanol bromide, 2-(p-dimethylaminostyryl)-1-ethylpyridiniumiodide, ethyl red, nigrosine, Savinyl Blue B™, Orasol Blue BLN™,Safranin O™, Azocarnum G™, Phenosafranine™, Azocarmine BX™, SolophenylBrilliant Blue BL™, Nile Blue A™, gallocyanine, gallamine blue,celestine blue, methylene green Azure A/B/C™, Blue VIF Organol™,Alizarin, Nitrofast Green GSB™, quinalizarine, Oil Blue N™, Solvaypurple, Ciba Blue™, Indigo Synthetic™, Chromophthal Bordeau RS™, AcidAlizarin Red B™, 5-amino-fluorescein, Rose Bengal™, Martius Yellow™,Chicago Blue 6B™, Alcian Blue 8GX™, cresyl violet,4,4-bis(dimethylamino)-benzylhydrolzinc phthalocyanine, Sudan III™,Pyronin Y™, Toluylene Blue™, cresyl violet perchlorate, Mendola's Blue™,Phosphine Dye, Nitron™, cresyl violet acetate, Ceres Orange R™,4-phenylazo-1-naphthyl-amine,4-(4-dimethylamino-1-naphthylazo)-3-methoxybenzene sulfonic acid,Bindschedler's Green™, and p-(p-dimethylaminophenylazo)-benzoic aciddissolved in and inert towards said solvent and adapted to change colorof the composition visible to the naked eye upon the change in state atsubstantially the predetermined temperature when so dissolved.
 2. Acomposition of matter substantially free of impurities, consistingessentially of a solid solution of:(a) a binary mixture ofortho-chloronitrobenzene and ortho bromonitrobenzene having a proportionof ortho-chloronitrobenzene to ortho bromonitrobenzene of about43.8:56.2 to about 4.0:96.0; and (b) an effective amount of an indicatormaterial selected from the group consisting of pinacyanol iodide,thionin, methylene blue, cresol red, neutral red iodide, neutral redchloride, crystal violet, acridin orange, Orasol Orange RLN™, OrasolNavy Blue™, Irgalith Red PR™, Fat Red BS™, Xylene Cyanol FF™, RhodamineB™, Rhodamine 6G™, Irgalith Magenta TCB™, Irgalith Pink TYNC™, ToluideneBlue O™, Savinyl Green B™, Savinyl Blue RS™, purpurin,3,3'-diethylthiadicarbocyanine iodide, cryptocyanine, Dicyanine A™,Merocyanine 540™, 4-(p-ethoxyphenylazo)-m-phenylene diaminehydrochloride, Yellow Orange S™, chrysoidan G™, fuchsin,aurintricarboxylic acid (ammonium salt), Victoria Blue R™, Pyronin G™,gallein, Erythrosin Yellow Blend™, chlorophenol blue, bromophenol blue,bromocresol purple, Coriphosphine O™, acriflavine, acridine orange,rhoduline violet, Alizarin Cyanine 2R™, Alizarin Red S™, alcanninn,Aurantia, Direct Green G™, Fast Salt Red 3GL™, Fast Salt Blue BB™, FastGarnet Salt GBC™, Carta Yellow G 180 0/0™, murexide, Savinyl Blue GLS™,Irgalith Blue GLSM™, phthalocyanine, Di Amingreen B™, Alizarin Blue S™,Celliton Blue Extra™ , neocyanine, Janus Green™, dimethyl yellow, FastYellow™, methyl red sodium salt, Alizarin Yellow R™, Eriochrome BlackT™, Chromotrope 2R™, Ponceau 6R™, Brilliant Ponceau G/R/2R™, chromolanyellow, Sudan Red B™, Bismark Brown G™, Fat Black™, Resorcin Brown™,Benzofast Pink 2BL™, Oil Red EGN™, Euroglancine, Fuchsin NB™,parafuchsin, Patent Blue™, Irgalith Blue TNC™, Phloxin B™, fluoresceinsodium salt, Rhodamine B base™, Eosin Scarlet, Eosin Yellowish,Erythrosin extra bluish, 4,5-dibromofluorescein, ethyleosin, Phloxin™,Cyanovin B™, chlorocresol green pinacyanol bromide,2-(p-dimethylaminostyryl)-1-ethylpyridinium iodide, ethyl red,nigrosine, Savinyl Blue B™, Orasol Blue BLN™, Safranin O™, Azocarnum G™,Phenosafranine™, Azocarmine BX™, Solophenyl Brilliant Blue BL™, NileBlue A™, gallocyanine, gallamine blue, celestine blue, methylene green,Azure A/B/C™, Blue VIF Organol™, Alizarin, Nitrofast Green GSB™,quinalizarine, Oil Blue N™, Solvay purple, Ciba Blue™, IndigoSynthetic™, Chromophthal Bordeau RS™, Acid Alizarin Red B™,5-aminofluorescein, Rose Bengal™, Martius Yellow™, Chicago Blue 6B™,Alcian Blue 8GX™, cresyl violet, 4,4-bis(dimethylamino)-benzylhydrol,zinc phthalocyanine, Sudan III™, Pyronin Y™, Toluylene Blue™, cresylviolet perchlorate, Mendola's Blue™, Phosphine Dye, Nitron™, cresylviolet acetate, Ceres Orange R™, 4-phenylazo-1-naphthylamine4-(4-dimethylamino-1-naphthylazo)-3-methoxybenzene sulfonic acid,Bindschedler's Green™, and p-(p-dimethylaminophenylazo)-benzoic aciddissolved in and inert towards said solvent mixture (a) and adapted tochange color of the composition visible to the naked eye upon the changein state from a solid state to a liquid state at a predeterminedtemperature.
 3. The composition of claim 1 or claim 2 wherein saidindicator material is pinacyanol iodide.
 4. The composition of claim 1or claim 2 wherein said indicator material is thionin.
 5. Thecomposition of claim 1 or claim 2 wherein said indicator material ismethylene blue.
 6. The composition of claim 1 or claim 2 wherein saidindicator material is cresol red.
 7. The composition of claim 1 or claim2 wherein said indicator material is neutral red iodide.
 8. Thecomposition of claim 1 or claim 2 wherein said indicator material isneutral red chloride.
 9. The composition of claim 1 or claim 2 whereinsaid indicator material is crystal violet.
 10. The composition of claim1 or claim 2 wherein said indicator material is acridin orange.
 11. Thecomposition of claim 1 or claim 2 wherein said indicator material isOrasol Orange RLN™.
 12. The composition of claim 1 or claim 2 whereinsaid indicator material is Orasol Navy Blue™.
 13. The composition ofclaim 1 or claim 2 wherein said indicator material is Irgalith Red PR™.14. The composition of claim 1 or claim 2 wherein said indicatormaterial is Fat Red BS™.
 15. The composition of claim 1 or claim 2wherein said indicator material is Xylene Cyanol FF™.
 16. Thecomposition of claim 1 or claim 2 wherein said indicator material isRhodamine B™.
 17. The composition of claim 1 or claim 2 wherein saidindicator material is Rhodamine 6G™.
 18. The composition of claim 1 orclaim 2 wherein said indicator material is Irgalith Magenta TCB™. 19.The composition of claim 1 or claim 2 wherein said indicator material isIrgalith Pink TYNC™.
 20. The composition of claim 1 or claim 2 whereinsaid indicator material is Toluidene Blue O™.
 21. The composition ofclaim 1 or claim 2 wherein said indicator material is Savinyl Green B™.22. The composition of claim 1 or claim 2 wherein said indicatormaterial is Savinyl Blue RS™.
 23. The composition of claim 1 or claim 2wherein said indicator material is purpurin.
 24. The composition ofclaim 1 or claim 2 wherein said indicator material is3,3'-diethylthiadicarbocyanine iodide.
 25. The composition of claim 1 orclaim 2 wherein said indicator material is cryptocyanine.
 26. Thecomposition of claim 1 or claim 2 wherein said indicator material isDicyanine A™.
 27. The composition of claim 1 or claim 2 wherein saidindicator material is Merocyanine 540™.
 28. The composition of claim 1or claim 2 wherein said indicator material is4-(p-ethoxyphenylazo)-m-phenylene diamine hydrochloride.
 29. Thecomposition of claim 1 or claim 2 wherein said indicator material isYellow Orange S™.
 30. The composition of claim 1 or claim 2 wherein saidindicator material is Chrysoidan G™.
 31. The composition of claim 1 orclaim 2 wherein said indicator material is fuchsin.
 32. The compositionof claim 1 or claim 2 wherein said indicator material isaurintricarboxylic acid (ammonium salt).
 33. The composition of claim 1or claim 2 wherein said indicator material is Victoria Blue R™.
 34. Thecomposition of claim 1 or claim 2 wherein said indicator material isPyronin G™.
 35. The composition of claim 1 or claim 2 wherein saidindicator material is gallein.
 36. The composition of claim 1 or claim 2wherein said indicator material is Erythrosin Yellow Blend™.
 37. Thecomposition of claim 1 or claim 2 wherein said indicator material ischlorophenol blue.
 38. The composition of claim 1 or claim 2 whereinsaid indicator material is bromophenol blue.
 39. The composition ofclaim 1 or claim 2 wherein said indicator material is bromocresolpurple.
 40. The composition of claim 1 or claim 2 wherein said indicatormaterial is Coriphosphine O™.
 41. The composition of claim 1 or claim 2wherein said indicator material is acriflavine.
 42. The composition ofclaim 1 or claim 2 wherein said indicator material is acridine orange.43. The composition of claim 1 or claim 2 wherein said indicatormaterial is rhoduline violet.
 44. The composition of claim 1 or claim 2wherein said indicator material is Alizarin Cyanine 2R™.
 45. Thecomposition of claim 1 or claim 2 wherein said indicator material isAlizarin Red S™.
 46. The composition of claim 1 or claim 2 wherein saidindicator material is alcannin.
 47. The composition of claim 1 or claim2 wherein said indicator material is Aurantia.
 48. The composition ofclaim 1 or claim 2 wherein said indicator material is Direct Green G™.49. The composition of claim 1 or claim 2 wherein said indicatormaterial is Fast Salt Red 3 GL™.
 50. The composition of claim 1 or claim2 wherein said indicator material is Fast Salt Blue BB™.
 51. Thecomposition of claim 1 or claim 2 wherein said indicator material isFast Garnet Salt GBC™.
 52. The composition of claim 2 wherein saidindicator material is Carta Yellow G 180 0/0™.
 53. The composition ofclaim 1 or claim 2 wherein said indicator material is murexide.
 54. Thecomposition of claim 1 or claim 2 wherein said indicator material isSavinyl Blue GLS™.
 55. The composition of claim 1 or claim 2 whereinsaid indicator material is Irgalith Blue GLSM™.
 56. The composition ofclaim 1 or claim 2 wherein said indicator material is phthalocyanine.57. The composition of claim 1 or claim 2 wherein said indicatormaterial is DiAmingreen B™.
 58. The composition of claim 1 or claim 2wherein said indicator material is Alizarin Blue S™.
 59. The compositionof claim 1 or claim 2 wherein said indicator material is Celliton BlueExtra™.
 60. The composition of claim 1 or claim 2 wherein said indicatormaterial is neocyanine.
 61. The composition of claim 1 or claim 2wherein said indicator material is Janus Green™.
 62. The composition ofclaim 1 or claim 2 wherein said indicator material is dimethyl yellow.63. The composition of claim 1 or claim 2 wherein said indicatormaterial is Fast Yellow™.
 64. The composition of claim 1 or claim 2wherein said indicator material is methyl red sodium salt.
 65. Thecomposition of claim 1 or claim 2 wherein said indicator material isAlizarin Yellow R™.
 66. The composition of claim 1 or claim 2 whereinsaid indicator material is Eriochrome Black T™.
 67. The composition ofclaim 1 or claim 2 wherein said indicator material is Chromoscope 2R™.68. The composition of claim 1 or claim 2 wherein said indicatormaterial is Ponceau 6R™.
 69. The composition of claim 1 or claim 2wherein said indicator material is Brilliant Ponceau G/R/2R™.
 70. Thecomposition of claim 1 or claim 2 wherein said indicator material ischromolan yellow.
 71. The composition of claim 1 or claim 2 wherein saidindicator material is Sudan Red B™.
 72. The composition of claim 1 orclaim 2 wherein said indicator material is Bismark brown G™.
 73. Thecomposition of claim 1 or claim 2 wherein said indicator material is FatBlack™.
 74. The composition of claim 1 or claim 2 wherein said indicatormaterial is Resorcin Brown™.
 75. The composition of claim 1 or claim 2wherein said indicator material is Benzofast Pink 2BL™.
 76. Thecomposition of claim 1 or claim 2 wherein said indicator material is OilRed EGN™.
 77. The composition of claim 1 or claim 2 wherein saidindicator material is Euroglaucine.
 78. The composition of claim 1 orclaim 2 wherein said indicator material is Fuchsin NB™.
 79. Thecomposition of claim 1 or claim 2 wherein said indicator material isparafuchsin.
 80. The composition of claim 1 or claim 2 wherein saidindicator material is Patent Blue™.
 81. The composition of claim 1 orclaim 2 wherein said indicator material is Irgalith Blue TNC™.
 82. Thecomposition of claim 1 or claim 2 wherein said indicator material isPhloxin B™.
 83. The composition of claim 1 or claim 2 wherein saidindicator material is fluorescein sodium salt.
 84. The composition ofclaim 1 or claim 2 wherein said indicator material is Rhodamine B base™.85. The composition of claim 1 or claim 2 wherein said indicatormaterial is Eosin Scarlet.
 86. The composition of claim 1 or claim 2wherein said indicator material is Eosin Yellowish.
 87. The compositionof claim 1 or claim 2 wherein said indicator material is Erythrosinextra bluish.
 88. The composition of claim 1 or claim 2 wherein saidindicator material is 4,5-dibromofluorescein.
 89. The composition ofclaim 1 or claim 2 wherein said indicator material is ethyleosin. 90.The composition of claim 1 or claim 2 wherein said indicator material isPhloxin™.
 91. The composition of claim 1 or claim 2 wherein saidindicator material is Cyanovin B™.
 92. The composition of claim 1 orclaim 2 wherein said indicator material is chlorocresol green.
 93. Thecomposition of claim 1 or claim 2 wherein said indicator material ispinacyanol bromide.
 94. The composition of claim 1 or claim 2 whereinsaid indicator material is 2-(p-dimethylaminostyryl)-1-ethyl pyridiniumiodide.
 95. The composition of claim 1 or claim 2 wherein said indicatormaterial is ethyl red.
 96. The composition of claim 1 or claim 2 whereinsaid indicator material is nigrosine.
 97. The composition of claim 1 orclaim 2 wherein said indicator material is Savinyl Blue B™.
 98. Thecomposition of claim 1 or claim 2 wherein said indicator material isOrasol Blue BLN™.
 99. The composition of claim 1 or claim 2 wherein saidindicator material is Safranin O™.
 100. The composition of claim 1 orclaim 2 wherein said indicator material is Azocarnum G™.
 101. Thecomposition of claim 1 or claim 2 wherein said indicator material isPhenosafranine™.
 102. The composition of claim 1 or claim 2 wherein saidindicator material is Azocarmine BX™.
 103. The composition of claim 1 orclaim 2 wherein said indicator material is Solophenyl Brilliant BlueBL™.
 104. The composition of claim 1 or claim 2 wherein said indicatormaterial is Nile Blue A™.
 105. The composition of claim 1 or claim 2wherein said indicator material is gallocyanine.
 106. The composition ofclaim 1 or claim 2 wherein said indicator material is gallamine blue.107. The composition of claim 1 or claim 2 wherein said indicatormaterial is celestin blue.
 108. The composition of claim 1 or claim 2wherein said indicator material is methylene green.
 109. The compositionof claim 1 or claim 2 wherein said indicator material is Azure A/B/C™.110. The composition of claim 1 or claim 2 wherein said indicatormaterial is Blue VIF Organol™.
 111. The composition of claim 1 or claim2 wherein said indicator material is Alizarin.
 112. The composition ofclaim 1 or claim 2 wherein said indicator material is Nitrofast GreenGSB™.
 113. The composition of claim 1 or claim 2 wherein said indicatormaterial is quinalizarine.
 114. The composition of claim 1 or claim 2wherein said indicator material is Oil Blue N™.
 115. The composition ofclaim 1 or claim 2 wherein said indicator material is Solvay purple.116. The composition of claim 1 or claim 2 wherein said indicatormaterial is Ciba Blue™.
 117. The composition of claim 1 or claim 2wherein said indicator material is Indigo Synthetic™.
 118. Thecomposition of claim 1 or claim 2 wherein said indicator material iscresol red.
 119. The composition of claim 1 or claim 2 wherein saidindicator material is chromophthal Bordeau RS™.
 120. The composition ofclaim 1 or claim 2 wherein said indicator material is Acid Alizarin RedB™.
 121. The composition of claim 1 or claim 2 wherein said indicatormaterial is 5-aminofluorescein.
 122. The composition of claim 1 or claim2 wherein said indicator material is Rose Bengal™.
 123. The compositionof claim 1 or claim 2 wherein said indicator material is MartiusYellow™.
 124. The composition of claim 1 or claim 2 wherein saidindicator material is Chicago Blue 6B™.
 125. The composition of claim 1or claim 2 wherein said indicator material is Alcian Blue 8GX™.
 126. Thecomposition of claim 1 or claim 2 wherein said indicator material iscresyl violet.
 127. The composition of claim 1 or claim 2 wherein saidindicator material is 4,4-bis(dimethylamino)-benzylhydrol.
 128. Thecomposition of claim 1 or claim 2 wherein said indicator material isZinc phthalocyanine.
 129. The composition of claim 1 or claim 2 whereinsaid indicator material is Sudan III™.
 130. The composition of claim 1or claim 2 wherein said indicator material is Pyronin Y™.
 131. Thecomposition of claim 1 or claim 2 wherein said indicator material isToluylene Blue™.
 132. The composition of claim 1 or claim 2 wherein saidindicator material is cresyl violet perchlorate.
 133. The composition ofclaim 1 or claim 2 wherein said indicator material is Mendola's Blue™.134. The composition of claim 1 or claim 2 wherein said indicatormaterial is Nitron™.
 135. The composition of claim 1 or claim 2 whereinsaid indicator material is cresyl violet acetate.
 136. The compositionof claim 1 or claim 2 wherein said indicator material is Ceres OrangeR™.
 137. The composition of claim 1 or claim 2 wherein said indicatormaterial is 4-phenylazo-1-naphthyl-amine.
 138. The composition of claim1 or claim 2 wherein said indicator material is4-(4-dimethylamino-1-naphthylazo) 3-methoxy benzene sulfonic acid. 139.The composition of claim 1 or claim 2 wherein said indicator material isBindschedler's Green™.
 140. The composition of claim 1 or claim 2wherein said indicator material is p-(p-dimethylaminophenylazo)-benzoicacid.